Prins reaction products of diisoamylene, derivatives thereof, organoleptic uses thereof and processes for preparing same

ABSTRACT

Described is the genus of compounds defined according to the structure: ##STR1## wherein one of the dashed lines represents a carbon-carbon double bond and each of the other of the dashed lines represent carbon-carbon single bonds; wherein the wavy line 
     represents a carbon-carbon single bond or no bond; wherein when the wavy line represents a carbon-carbon single bond, Z represents methylene and when the wavy line represents no bond, Z represents hydrogen or C 2  -C 4  acyl prepared according to a Prins reaction between diisoamylene defined according to the structure: ##STR2## wherein one of the dashed lines represents a carbon-carbon double bond and each of the other of the dashed lines represent carbon-carbon single bonds or one of the structures: ##STR3## formaldehyde of a formaldehyde source such as trioxane or paraformaldehyde in the presence of an acyl anhydride and an acid catalyst; and organoleptic uses of such Prins reaction products in the field of perfumery, colognes, perfumed articles, foodstuffs, chewing gums, medicinal products, toothpastes, chewing tobaccos and smoking tobaccos.

This is a divisional of application Ser. No. 492,011, filed May 5, 1983,now U.S. Pat. No. 4,495,359, which, in turn, is a streamline divisionalof U.S. Letters Patent, Ser. No. 391,583 filed on June 24, 1982, nowU.S. Pat. No. 4,429,156 which, in turn, is a streamline divisional ofU.S. Letters Patent, Ser. No. 267,850 filed on May 28, 1981, now U.S.Pat. No. 4,359,412 issued Nov. 16, 1982.

BACKGROUND OF THE INVENTION

The instant invention relates to compounds having the genus: ##STR4##wherein one of the dashed lines represents a carbon-carbon double bondand each of the other of the dashed lines represent carbon-carbon singlebonds; wherein the wavy line represents a carbon-carbon single bond orno bond; wherein when the wavy line represents a carbon-carbon singlebond, Z represents methylene and when the wavy line represents no bond,Z represents hydrogen or C₂ -C₄ acyl and includes compounds definedaccording to the structure: ##STR5## wherein R represents hydrogen or C₂-C₄ acyl and compounds defined according to the structure: ##STR6##wherein in each of the compound genera, one of the dashed linesrepresents a carbon-carbon double bond and each of the other of thedashed lines represent carbon-carbon single bonds.

Inexpensive chemical compounds which can provide intense andlong-lasting woody, ionone-like, fruity, floral, amber, cedarwood,varoris-like, peach, coriander-like, citrusy, oriental and minty aromanuances are desirable in the art of perfumery. Many of the naturalmaterials which provide such fragrances and contribute such desirednuances to perfumery compositions are high in cost, unobtainable attimes, vary in quality from one batch to another and/or are generallysubject to the usual variations of natural products.

There is, accordingly, a continuing effort to find synthetic materialswhich will replace, enhance or augment the fragrance notes provided bynatural essential oils or compositions thereof. Unfortunately, many ofthe synthetic materials either have the desired nuances only to arelatively small degree, or they contribute undesirable or unwanted odorto the compositions.

In addition, there is a continuing search for food flavor compositionswhich can vary, fortify, modify, enhance, augment or otherwise improvethe flavor and/or aroma of foodstuffs, medicinal products, toothpastes,chewing gums and chewing tobaccos. To be satisfactory, such compositionsshould be stable, non-toxic and blendable with other ingredients toprovide their own unique flavor and aroma nuances without detractingfrom the co-ingredients of the formulations in which they are used.Preferably, such compositions should be naturally occurring or presentin natural foodstuffs so that their ingestible safety can be readilyrecognized. These materials should be capable of being synthesized in asimple and economical manner. Thus, the need for safe flavors in theraisin and rum flavor area is well known particularly in the ice cream,chewing tobacco and yogurt flavor areas. More specifically, there is aneed for the development of non-toxic materials which can replacenatural materials not readily available, having sweet, floral,coriander-like, fruity, cedarwood-like and oriental aromacharacteristics with sweet, vanilla-like, floral, fruity,coriander-like, cedarwood and raisin-like flavoring characteristics.

In the tobacco flavoring art (pertaining to tobaccos and substitutetobaccos), there is a considerable need for substituents havingoriental, fruity, rum-like, and Turkish tobacco-like aroma and tastenuances both prior to and on smoking in the main stream and in the sidestream. Specifically described herein are materials having such anorganoleptic profile but which are stable with respect to time.

The instant invention provides the foregoing, which the prior art hasheretofore failed to provide. Furthermore, the compounds definedaccording to the genus: ##STR7## have unobvious, unexpected andadvantageous organoleptic properties (wherein one of the dashed linesrepresents a carbon-carbon double bond and each of the other of thedashed lines represent carbon-carbon single bonds; wherein the wavy linerepresents a carbon-carbon single bond or no bond; wherein when the wavyline represents a carbon-carbon single bond, Z represents methylene andwhen the wavy line represents no bond, Z represents hydrogen or C₂ -C₄acyl).

The compounds defined according to the genus: ##STR8## wherein one ofthe dashed lines represents a carbon-carbon double bond and each of theother of the dashed lines represent carbon-carbon single bonds; whereinthe wavy line represents a carbon-carbon single bond or no bond; whereinwhen the wavy line represents a carbon-carbon single bond, Z representsmethylene and when the wavy line represents no bond, Z representshydrogen or C₂ -C₄ acyl are prepared according to the "Prins" reaction,which reaction, basically, involves the reaction of an olefinic doublebond-containing compound with formaldehyde or a formaldehyde precursoror formaldehyde source such as trioxane, paraformaldehyde or formalin.

Perfumery compounds are known to have been produced using the Prinsreaction. Thus, the paper entitled "The Olefin-Aldehyde Condensation/ThePrins Reaction" by Arundale and Mikeska, Chem. Reviews, 51, 505-55 1952,discloses the reaction to form Nopol acetate, thusly: ##STR9## whereinin the reaction, when glacial acetic acid is added to the reaction mass,the Nopol acetate is formed; yet without the use of glacial acetic acid,Nopol itself is formed.

U.S. Pat. No. 4,100,110 issued on July 11, 1978 (Class 252, subclass522) discloses compounds for use in perfumery which are obtained byperforming a Prins reaction on longifolene including primary andsecondary alcohols, their esters and corresponding aldehydes andketones. Specifically, in Example 1, column 7 of U.S. Pat. No. 4,100,110discloses the preparation of compounds having the structures: ##STR10##for use in perfumery as a result of their cedarwood-vetiver aroma.

The compounds of the prior art and processes of the prior art aredifferent in kind and yield materials having organoleptic propertiesdifferent in kind from the compounds of the instant invention.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. AA represents the GLC profile for the reaction product of Example Ausing a 70% sulfuric acid catalyst at 35° C.

FIG. AB represents the GLC profile for the reaction product of Example Ausing an Amberlyst® 15 acidic ion exchange resin catalyst at atemperature of 150° C.

FIG. AC represents the GLC profile for the reaction product of Example Ausing an Amberlyst® 15 catalyst at 100° C.

FIG. AD represents the GLC profile for the reaction product of Example Ausing a sulfuric acid catalyst and an alpha-methyl styrene diluent at35° C. according to the conditions of United Kingdom PatentSpecification No. 796,130 (crude reaction product).

FIG. AE represents the GLC profile for the reaction product of Example Ausing a sulfuric acid catalyst at 35° C. and an alpha-methyl styrenediluent according to the conditions of United Kingdom PatentSpecification No. 796,130 (distilled reaction product).

FIG. BA represents the NMR spectrum for peak 1 of the GLC profile ofFIG. AE. Peak 1 has been determined by analysis to be the compoundhaving the structure: ##STR11##

FIG. BB represents the infra-red spectrum for peak 1 of the GLC profileof FIG. AE.

FIG. CA represents the NMR spectrum for peak 2 of the GLC profile ofFIG. AE. Peak 2 contains the compounds having the structures: ##STR12##

FIG. CB represents the infra-red spectrum for peak 2 of the GLC profileof FIG. AE.

FIG. D represents the NMR spectrum for peak 2 of the GLC profile of FIG.AB.

FIG. 1 is the GLC profile for the reaction product produced according toExample I containing a mixture of compounds defined according to thegeneric structure: ##STR13## wherein in the mixture in each of themolecules, one of the dashed lines represents a carbon-carbon doublebond and each of the other of the dashed lines represent carbon-carbonsingle bonds.

FIG. 2 is the GLC profile for fraction 8 of the distillation product ofthe reaction product of Example I containing a mixture of compoundsdefined according to the generic structure: ##STR14## wherein in each ofthe molecules in the mixture, one of the dashed lines represents acarbon-carbon double bond and each of the other of the dashed linesrepresent carbon-carbon single bonds.

FIG. 3 is the NMR spectrum for the reaction product of Example Icontaining a mixture of compounds defined according to the genus:##STR15## wherein in each of the molecules of this genus, one of thedashed lines represents a carbon-carbon double bond and each of theother of the dashed lines represent carbon-carbon single bonds.

FIG. 4 is the infra-red spectrum for the reaction product of Example Icontaining a mixture of compounds defined according to the genus:##STR16## wherein in each of the molecules of the genus, one of thedashed lines represents a carbon-carbon double bond and each of theother of the dashed lines represent carbon-carbon single bonds.

FIG. 5 is the GLC profile for the reaction product of Example IIcontaining a mixture of compounds defined according to the genus:##STR17## wherein in each of the molecules of the genus, one of thedashed lines represents a carbon-carbon double bond and each of theother of the dashed lines represent carbon-carbon single bonds.

FIG. 6 is the NMR spectrum for fraction 7 of the distillation product ofthe reaction product of Example II wherein there is present a mixturedefined according to the genus: ##STR18## wherein in each of themolecules of the genus, one of the dashed lines is a carbon-carbondouble bond and each of the other of the dashed lines representcarbon-carbon single bonds.

FIG. 7 is the infra-red spectrum for the reaction product of Example IIcontaining a mixture of compounds defined according to the genus:##STR19## wherein in each of the molecules of the genus, one of thedashed lines represents a carbon-carbon double bond and each of theother of the dashed lines represent carbon-carbon single bonds.

FIG. 8 is the GLC profile for the reactin product of Example IIIcontaining a mixture of compounds defined according to the genus:##STR20## wherein in each of the molecules of the genus, one of thedashed lines represents a carbon-carbon double bond and each of theother of the dashed lines represent carbon-carbon single bonds.

FIG. 9 is the NMR spectrum for the reaction product of Example IIIcontaining a mixture of compounds defined according to the genus:##STR21## wherein in the genus in each of the molecules, one of thedashed lines represents a carbon-carbon double bond and each of theother of the dashed lines represent carbon-carbon single bonds.

FIG. 10 is the infra-red spectrum for the reaction product of ExampleIII containing a mixture of compounds defined according to the genus:##STR22## wherein in the genus in each of the molecules, one of thedashed lines represents a carbon-carbon double bond and each of theother of the dashed lines represent carbon-carbon single bonds.

FIG. 11 is the GLC profile for bulked fractions 1-6 of the distillationproduct of the reaction product of Example IV containing a mixture ofcompounds defined according to the genus: ##STR23## wherein in the genusin each of the molecules, one of the dashed lines represents acarbon-carbon double bond and each of the other of the dashed linesrepresent carbon-carbon single bonds.

FIG. 12 is the NMR spectrum for the major peak in the GLC profile ofFIG. 11 which consists of the compound having the structure: ##STR24##

FIG. 13 is the IR spectrum for the major component of the GLC profile ofFIG. 11 produced according to Example IV consisting of the compoundhaving the structure: ##STR25##

FIG. 14 is the GLC profile for fraction 2 of the distillation product ofthe reaction product of Example V(A) containing a mixture of compoundsdefined according to the genus: ##STR26## wherein in each of themolecules of the genus, one of the dashed lines represents acarbon-carbon double bond and each of the other of the dashed linesrepresent carbon-carbon single bonds.

FIG. 15 is the GLC profile for fraction 9 of the distillation product ofthe reaction product of Example V(A) containing a mixture of compoundsdefined according to the genus: ##STR27## wherein in each of themolecules of the genus, one of the dashed lines represents acarbon-carbon double bond and each of the other of the dashed linesrepresent carbon-carbon single bonds.

FIG. 16 is the NMR spectrum for the reaction product of Example V(A)containing a mixture of compounds defined according to the genus:##STR28## wherein in each of the molecules of the genus, one of thedashed lines represents a carbon-carbon double bond and each of theother of the dashed lines represent carbon-carbon single bonds.

FIG. 17 is the infra-red spectrum for peak 2 of the GLC profile of FIG.14 containing a mixture of compounds (produced by the reaction set forthin Example V(A)) defined according to the genus: ##STR29## wherein ineach of the molecules of the genus, one of the dashed lines represents acarbon-carbon double bond and each of the other of the dashed linesrepresent carbon-carbon single bonds.

FIG. 18 is the infra-red spectrum for the reaction product of ExampleV(B).

RELATED PATENT APPLICATIONS

    ______________________________________                                         Ser. No.                                                                             Filing Date Title                                                     ______________________________________                                        233,861                                                                              February 12, 1981                                                                          "ALIPHATIC C.sub.11 BRANCHED                                                  CHAIN ALDEHYDES AND                                                           ALCOHOLS, PROCESS FOR                                                         PREPARING SAME AND                                                            USES THEREOF IN AUGMEN-                                                       TING OR ENHANCING THE                                                         AROMA OF PERFUMES,                                                            COLOGNES AND/OR                                                               PERFUMED ARTICLES"                                        212,887                                                                              December 4, 1980                                                                           "BRANCHED CHAIN OLE-                                                          FINIC ALCOHOLS, THIOLS,                                                       ESTERS AND ETHERS,                                                            ORGANOLEPTIC USES                                                             THEREOF, PROCESSES FOR                                                        PREPARING SAME AND                                                            INTERMEDIATES                                                                 THEREFOR"                                                        April 9, 1981                                                                              "BRANCHED CHAIN OLE-                                                          FINIC ALCOHOLS, THIOLS,                                                       ESTERS AND ETHERS,                                                            ORGANOLEPTIC USES                                                             THEREOF, PROCESSES FOR                                                        PREPARING SAME AND                                                            INTERMEDIATES                                                                 THEREFOR"                                                 ______________________________________                                    

THE INVENTION

The present invention provides compounds defined according to thegeneric structure: ##STR30## wherein one of the dashed lines representsa carbon-carbon double bond and each of the other of the dashed linesrepresent carbon-carbon single bonds; wherein the wavy line represents acarbon-carbon single bond or no bond at all; when the wavy linerepresents a carbon-carbon single bond, Z represents --CH₂ --and whenthe wavy line represents no bond at all, Z represents hydrogen, or C₂-C₄ acyl. Thus, more specifically, when the wavy line represents acarbon-carbon single bond, the genus is more specific in the structure:##STR31## wherein one of the dashed lines represents a carbon-carbondouble bond and each of the other of the dashed lines representcarbon-carbon single bonds; and where the wavy line represents no bondat all, the genus is represented by the structure: ##STR32## wherein Rrepresent hydrogen or C₂ -C₄ acyl and one of the dashed lines representsa carbon-carbon double bond and each of the other of the dashed linesrepresent carbon-carbon single bonds.

Collectively, the genus defined according to the structure: ##STR33##wherein the dashed lines, wavy line and the Z are defined as above, iscalled "one or more Prins reaction products".

The Prins reaction products of our invention produced according to theprocess of our invention are capable of augmenting or enhancing sweet,floral, coriander-like, fruity, cedarwood and oriental aromacharacteristics and sweet, vanilla-like, floral, fruity, coriander-like,cedarwood-like and raisin taste characteristics of foodstuffs, foodstuffflavors, chewing gums, chewing gum flavors, chewing tobaccos, chewingtobacco flavors, medicinal products, medicinal product flavors,toothpastes and toothpaste flavors.

The Prins reaction products of our invention as well as mixtures thereofare also capable of modifying or enhancing the aroma characteristics ofperfume compositions, colognes and perfumed articles (including soaps,nonionic, anionic, cationic and zwitterionic detergents and fabricsoftener articles) by imparting thereto woody, ionone-like, fruity,floral, amber, cedarwood-like, vanoris-like, peach, coriander-like,oriental, citrusy and minty aroma nuances, thus fulfilling a need in thefield of perfumery.

In tobacco, tobacco flavoring, substitute tobacco and substitute tobaccoflavoring compositions, the Prins reaction products of our inventionproduced according to the process of our invention impart oriental,fruitwood-like, rum-like, and Turkish tobacco-like aroma and tastenuances to smoking tobacco and substitute smoking tobaccos prior to andon smoking in both the main stream and the side stream.

The Prins reaction is carried out on diisoamylene with formaldehyde or aformaldehyde precursor such as formalin or paraformaldehyde in thepresence of or in the absence of an acyl anhydride and in the presenceof an acid catalyst; either a Lewis acid such as borontrifluorideetherate or stannic chloride or the like, or a protonic acid such assulfuric acid or phosphoric acid.

Depending on whether an acyl anhydride is used or not; and depending onwhether a protonic acid or a Lewis acid catalyst is used; and dependingupon whether formaldehyde or trioxane or paraformaldehyde is used as aprecursor reactant, the resulting product encompassed within the genericstructure: ##STR34## wherein one of the dashed lines represents acarbon-carbon double bond and each of the other of the dashed linesrepresent carbon-carbon single bonds; wherein the wavy line represents acarbon-carbon single bond or no bond; wherein when the wavy linerepresents a carbon-carbon single bond, Z represents methylene and whenthe wavy line represents no bond, Z represents hydrogen or C₂ -C₄ acyl,will be different; that is, it will be either one of the compoundsencompassed by the generic structure: ##STR35## wherein R representshydrogen or wherein R represents C₂ -C₄ acyl or it will be one of thegeneric structures defined according to the structure: ##STR36## whereinone of the dashed lines represents a carbon-carbon double bond andwherein each of the other of the dashed lines represent carbon-carbonsingle bonds.

With respect to the diisoamylene precursor, "diisoamylene" is a dimer ofisoamylene wherein the dimerization takes place in the presence of acid."Diisoamylene" is indicated to be synthesized in the followingreferences:

(i) Murphy & Lane, Ind. Eng. Chem., Prod. Res. Dev., Vol. 14, No. 3,1975 p. 167 (Title: Oligomerization of 2-Methyl-2-Butene in SulfuricAcid and Sulfuric-Phosphoric Acid Mixtures).

(ii) Whitmore & Mosher, Vol. 68, J. Am. Chem. Soc., February, 1946, p.281 (Title: The Depolymerization of 3,4,5,5-Tetramethyl-2-hexene and3,5,5-Trimethyl-2-heptane in Relation to the Dimerization ofIsoamylenes).

(iii) Whitmore & Stahly, Vol. 67, J. Am. Chem. Soc., December, 1945, p.2158 (Title: The Polymerization of Olefins. VIII The Depolymerization ofOlefins in Relation to Intramolecular Rearrangements. II).

(iv) U.S. Pat. No. 3,627,700, issued on Dec. 14, 1971, (Zuech).

(v) U.S. Pat. No. 3,538,181, issued on Nov. 3, 1970 (Banks).

(vi) U.S. Pat. No. 3,461,184, issued on Aug. 12, 1969 (Hay, et al).

(vii) Gurwitsch, Chemische Berichte, 1912, Vol. 2, p. 796 (Production ofDi-isoamylene from Isoamylene Using Mercury Acetate Catalyst).

United Kingdom Pat. No. 796,130 published on June 4, 1958 discloses thesynthesis of polyalkylindanes by means of, interalia, reactingalpha-methylstyrene with trimethylethene (2-methyl-butene-2) in thepresence of an acid catalyst such as, sulfuric acid or boron trifluorideetherate. It is further indicated that such compounds are usefulintermediates in the production of perfumery compounds. Apparently,however, the more volatile diisoamylenes produced as side-products inthe reaction of 2-methyl-butene-2 with alpha-methylstyrene haveheretofore been discarded.

The "formaldehyde" precursor is shown as having the structure: ##STR37##yet, in place of formaldehyde itself, trioxane having the structure:##STR38## or paraformaldehyde having the structure: ##STR39## wherein Xis an integer of from 2 up to 40 may be used in place of formaldehyde.Whenever formaldehyde having the structure: ##STR40## is shown in areaction with quotation marks around it thusly, it is intended that thisparticular term mean either formaldehyde itself or trioxane orparaformaldehyde or formalin or any other form of formaldehyde.

When the Prins reaction of my invention is carried out usingparaformaldehyde as a precursor with the diisoamylene and using a Lewisacid catalyst such as borontrifluoride etherate, stannic chloride, zincchloride, zinc bromide, diethyl aluminum chloride, aluminum diethylchloride, or the like, and in the presence of an acyl anhydride havingthe structure: ##STR41## wherein R₁ and R₂ may be the same or differentand each represents C₁ -C₃ alkyl, a compound having the structure:##STR42## wherein R₁₂ represents R₁ or R₂ and one of the dashed lines inthe resulting material is a carbon-carbon double bond and each of theother of the dashed lines are carbon-carbon single bonds.

When the reaction is carried out using formaldehyde per se, rather thanparaformaldehyde, however, even in the presence of a Lewis acid catalystsuch as stannic chloride or boron trifluoride etherate, and even in thepresence of an acyl anhydride having the structure: ##STR43## thecompound that is formed is an alcohol defined according to the genericstructure: ##STR44## wherein one of the dashed lines represents acarbon-carbon double bond and each of the other of the dashed linesrepresent carbon-carbon single bonds.

When the reaction is carried out using formaldehyde alone, in theabsence of an acyl anhydride, the reaction product is also the alcoholdefined according to the structure: ##STR45## however, the alcohol atthis particular point is formed in yields lower than that when comparedto the reaction carried out first forming the ester having thestructure: ##STR46## and then hydrolyzing this ester having thestructure: ##STR47## to form the alcohol having the structure: ##STR48##wherein in each of the molecules, one of the dashed lines represents acarbon-carbon double bond and each of the other of the dashed linesrepresent carbon-carbon single bonds.

Once the ester having the generic structure: ##STR49## is formed,wherein R₁₂ represents R₁ and R₂ and each are the same or different andeach represents C₁ -C₃ alkyl, this material may be hydrolyzed in thepresence of base to form, in relatively high yields, a mixture ofcompounds defined according to the structure: ##STR50##

However, when using in place of a Lewis acid catalyst, a protonic acidcatalyst such as sulfuric acid or phosphoric acid, even when using anacyl anhydride having the structure: ##STR51## the reaction productrather than having the structure: ##STR52## wherein R is hydrogen or C₂-C₄ acyl, is cyclic in nature having the structure: ##STR53## whereby 2moles of formaldehyde react with 1 mole of diisoamylene to form suchmolecules having the structure: ##STR54## rather than the case where 1mole of formaldehyde reacts as is the case in the presence of the Lewisacid catalyst forming the structure: ##STR55##

Where one of the compounds defined according to the structure: ##STR56##is formed wherein R₁₂ represents C₁ -C₃ alkyl and one of the dashedlines represents a carbon-carbon double bond and the other of the dashedlines represent carbon-carbon single bonds, this compound may be used"as is" for its organoleptic properties or it may be hydrolyzed in thepresence of base to form one of the compounds defined according to thegenus: ##STR57## wherein one of the dashed lines represents acarbon-carbon double bond and the other of the dashed lines representcarbon-carbon single bonds. Again, this compound can be used "as is" forits organoleptic properties or it may be re-esterified with anotheralkanoic acid anhydride having the structure: ##STR58## wherein R₃ andR₄ are the same or different and each represents C₁ -C₃ alkyl wherebyone of the compounds defined according to the structure: ##STR59## isformed wherein R₃₄ is C₁ -C₃ alkyl and one of the dashed linesrepresents a carbon-carbon double bond and each of the other of thedashed lines represent carbon-carbon single bonds.

Thus, the reaction sequences encompassed by my invention are as follows:

(a) The reaction of the alkanoic acid anhydride with diisoamylene andformaldehyde in the presence of a Lewis acid catalyst to form the C₁₁alcohol ester thusly: ##STR60## wherein R₁ and R₂ are the same ordifferent and each represents C₁ -C₃ alkyl; wherein R₁₂ is R₁ or R₂ andrepresents C₁ -C₃ alkyl and wherein one of the dashed lines represents acarbon-carbon double bond and each of the other of the dashed linesrepresent carbon-carbon single bonds;

(b) The hydrolysis reaction: ##STR61## wherein R₁₂ and the dashed linesare defined as above; (c) The re-esterification reaction: ##STR62##wherein one of the dashed lines represents a carbon-carbon double bondand each of the other of the dashed lines represent carbon-carbon singlebonds and wherein R₃ and R₄ are the same or different C₁ -C₃ alkyl; andwherein R₃₄ is R₃ or R₄ and represents C₁ -C₃ alkyl; and

(d) The reaction of the diisoamylene with formaldehyde and an alkanoicacid anhydride in the presence of a protonic acid catalyst thusly:##STR63## wherein one of the dashed lines represents a carbon-carbondouble bond and the other of the dashed lines represent carbon-carbonsingle bonds.

In the esterification reaction: ##STR64## the Lewis acid may beborontrifluoride etherate, stannic chloride, zinc chloride, zincbromide, ethyl aluminum dichloride, diethyl aluminum chloride, oraluminum trichloride. R₁ and R₂ may be the same or different and eachrepresents C₁ -C₃ alkyl such as methyl, ethyl, isopropyl or n-propyl.The formaldehyde used may be and is preferably paraformaldehyde,however, trioxane may also be used. Formaldehyde itself or formalinshould not be used if the ester is attempted to be formed since lowyields of alcohol will be formed rather than the ester in accordancewith the reaction: ##STR65## Trioxane has the structure: ##STR66##Paraformaldehyde is indicated by the structure: ##STR67##

The mole ratio of diisoamylene:formaldehyde (as paraformaldehyde or astrioxane) may vary from about 1:2 up to about 2:1 with a preferred moleratio of about 1:1. The mole ratio of acyl anhydride:diisoamylene mayvary from about 1:1 up to about 2:1 acyl anhydride:diisoamylene with apreferred mole ratio of 1.4-1.5:1 of acyl anhydride:diisoamylene. Theconcentration of diisoamylene in the reaction mass is preferably fromabout 1 mole per liter up to about 5 moles per liter.

The concentration of Lewis acid in the reaction mass may vary from about0.01 moles per liter up to about 0.5 moles per liter.

The reaction temperature may vary from about 50° C. up to about 150° C.depending on the pressure above the reaction mass and depending upon thetime desired to complete the reaction for a given particular yield. Whenhigher temperatures are used, the time of reaction required forcompletion is shorter, however, the yield is lower and the quantity ofby-product formed is greater. The most desirable reaction temperaturevaries between 80° and 110° C. It is most preferable to carry out thereaction at atmospheric pressure. Higher reaction pressures or lowerreaction pressures do not give rise to a higher yield or higherconversion rate.

At the end of the reaction, the reaction mass may be "worked-up" in theusual way by means of, for example, distillation or chromatographicseparation, e.g. commercial high-pressure liquid chromatography.

In carrying out the hydrolysis reaction to form the C₁₁ unsaturatedalcohol thusly: ##STR68## the mole ratio of ester having the structure:##STR69## to alkali metal hydroxide, e.g., potassium hydroxide, sodiumhydroxide or lithium hydroxide, may vary from about 1:2 up to about 2:1with an excess of alkali metal hydroxide being preferred. That is, it ispreferred that the mole ratio of alkali metal hydroxide:ester having thestructure: ##STR70## be about 2:1. It is preferred that the hydrolysisreaction to form the compound having the structure: ##STR71## be carriedout using highly concentrated base, e.g., from about 30% up to about 50%concentration. Concentration of ester having the structure: ##STR72## inthe reaction mass may vary from about 2 moles per liter up to about 8moles per liter with a concentration of 2-3 moles per liter of esterhaving the structure: ##STR73## being preferred. The concentration ofcaustic is preferably double the concentration of ester. Thus, theconcentration of caustic may vary from about 3 moles per liter up toabout 10 moles per liter with a preferred concentration of caustic beingabout 5 moles per liter. The temperature of hydrolysis is preferablybetween about 50° C. up to about 80° C. with a hydrolysis temperature of65° C. being preferred, at atmospheric pressure. Pressures aboveatmospheric pressure or below atmospheric pressure may be used for thehydrolysis reaction by using higher or lower pressures does not giverise to any advantage insofar as yield or conversion per unit time isconcerned. Indeed, most economically, the reaction pressure for thishydrolysis reaction is preferably 1 atmosphere.

At the end of the hydrolysis reaction, the reaction mass may beappropriately worked up as by pH adjustment and fractional distillationthereby yielding the C₁₁ unsaturated alcohol having one of thestructures: ##STR74## wherein one of the dashed lines represents acarbon-carbon double bond and each of the other of the dashed linesrepresent carbon-carbon single bonds.

If desired, the re-esterification reaction which may be representedthusly: ##STR75## takes place wherein R₃ and R₄ are the same ordifferent and each represents C₁ -C₃ alkyl and R₃₄ represents one of R₃or R₄ and represents C₁ -C₃ alkyl. The re-esterification is usuallycarried out in order to create a higher yield of ester than thatpreviously formable by means of the original reaction of acyl anhydride.Thus, if the initial reaction is carried out with acetic anhydride andit is ultimately desired to produce the propionate ester or theisobutyrate ester, then the most desirable route to take is to firstform the acetate estate; then hydrolyze same and finally react the C₁₁unsaturated alcohol with propionic anhydride according to the reaction:##STR76##

The mole ratio of acyl anhydride:C₁₁ unsaturated alcohol may vary fromabout 1:1 up to about 3:1 with a mole ratio of acyl anhydride, e.g.,n-propionic anhydride:C₁₁ unsaturated alcohol of 2:1 being preferred.

The temperature of the esterification reaction, if carried out atatmospheric pressure, is preferably between 100° and 120° C. Higherpressures of reaction, that is, higher than atmospheric, are neitherdesired nor are they advantageous. By the same token, lower pressures ofreaction are neither desired nor advantageous insofar as yield orconversion of reaction product.

At the end of the reaction, the reaction mass is worked up in the usualmanner by first neutralizing the excess alkanoic acid anhydride withcaustic and then neutralizing the reaction mass. The reaction mass isthen distilled through a fractional distillation column to yield productacceptable from an organoleptic standpoint.

In carrying out the Prins reaction to form the cyclic ether, accordingto the reaction: ##STR77## it is prefereed that as a formaldehydesource, paraformaldehyde be used. Furthermore, it is preferred that theacid catalyst be concentrated sulfuric acid or concentrated phosphoricacid or concentrated paratoluene sulfonic acid or concentrated methanesulfonic acid.

The reaction may be carried out using a mole ratio of effectiveformaldehyde (as paraformaldehyde):diisoamylene of from 2:1 up to 1:2with an effective mole ratio of formaldehyde:diisoamylene which ispreferred being 2:1. The concentration of sulfuric acid or phosphoricacid or methane sulfonic acid or other protonic acid in the reactionmass, may vary from about 0.01 moles per liter up to about 1 mole perliter with a preferred concentration of protonic acid catalyst beingfrom 0.1 up to 0.2 moles per liter. The mole ratio of acyl anhydride,perferably acetic anhydride: diisoamylene may vary from about 1:4 up toabout 1:1 with a preferred mole ratio of acyl anhydride:diisoamylenebeing about 1:2. The reaction temperature may vary from about 50° C. upto about 120° C. but the preferred reaction temperature is 85°-95° C.

The reaction can be carried out at atmospheric pressure,super-atmospheric or sub-atmospheric pressure. No advantage existseither in conversion or yield when using super-atmospheric orsub-atmospheric pressure. Accordingly, it is most expeditious to utilizeatmospheric pressures and a reaction temperature of from about 85° up to95° C. in this reaction.

The following table sets forth the reaction products of my invention andthe corresponding organoleptic properties:

                                      TABLE I                                     __________________________________________________________________________    Structure of     Perfume  Food Flavor                                                                            Tobacco Flavor                             Reaction Product Properties                                                                             Properties                                                                             Properties                                 __________________________________________________________________________     ##STR78##       A woody, ionone- like, fruity and floral aroma with                           oriental nuances.                                                                      Raspberry seed aroma and taste.                                                        An oriental, fruit, rum-like and                                              Turkish tobacco-like aroma and taste                                          prior to and on smoking in the main                                           stream and                                 Mixture produced                   the side stream                            according to Example                                                          I wherein in each of                                                          the molecules, one                                                            of the dashed lines                                                           represents a carbon-                                                          carbon double bond                                                            and each of the other                                                         of the dashed lines                                                           represent carbon-                                                             carbon single bonds.                                                           ##STR79##       A woody, amber and floral aroma with minty                                    and oriental-like nuances.                                                             A minty and raspberry seed- like aroma and                                    taste.   An oriental, Turkish tobacco- like                                            aroma and taste both prior to and on                                          smoking in the main stream and the         A mixture produced                 side stream                                according to Example II                                                       wherein in each of the                                                        molecules, one of the                                                         dashed lines represents                                                       a carbon-carbon double                                                        bond and each of the                                                          other of the dashed lines                                                     represents carbon-carbon                                                      single bonds.                                                                  ##STR80##       A fruity, floral, woody and cedar- wood aroma with amber                      and oriental topnotes.                                                                 An intense, strawberry/rasp- berry aroma and                                  taste.   A fruity, rum- like aroma and taste                                           both prior to and on smoking in the                                           main stream and the side stream.           Mixture produced                                                              according to Example III                                                      wherein in each of the                                                        molecules of the mixture,                                                     one of the dashed lines                                                       represents a carbon-                                                          carbon double bond and                                                        each of the other of the                                                      dashed lines represents                                                       a carbon-carbon single                                                        bond.                                                                          ##STR81##       A fruity vanoris- like, peach-like, coriander-like,                           cedarwood and oriental aroma.                                                          A sweet, floral, coriander-like, fruity,                                      cedarwood and oriental aroma with a sweet                                     vanalin- fruity; coriander- like cedarwood and                                raisin taste                                                                           An oriental, fruity, rum-like, Turkish                                        tobacco- like aroma and taste both                                            prior to and on smoking in the main                                           stream and the side stream.                Mixture produced          causing it to be                                    according to Example IV   useful in raisin                                    wherein in each of the    and rum flavors.                                    molecules of the mixture,                                                     one of the dashed lines                                                       represents a carbon-                                                          carbon double bond and                                                        each of the other of the                                                      dashed lines represent                                                        carbon-carbon single                                                          bonds.                                                                         ##STR82##       A woody, ionone- like, oriental and citrusy aroma with                        minty topnotes.                                                                        An intense, minty and citrus fruit and lemon                                  peel aroma and taste.                                                                  A woody, cigar box, Turkish tobacco-lik                                       e aroma and taste both prior to and on                                        smoking in the main stream and the                                            side stream.                               Mixture produced                                                              according to Example V                                                        wherein in each of the                                                        molecules of the mixture                                                      one of the dashed lines                                                       represents a carbon-                                                          carbon double bond and                                                        each of the other of                                                          the dashed lines                                                              represents carbon-                                                            carbon single bonds.                                                          __________________________________________________________________________

When the Prins reaction products produced according to the process of myinvention are used as food flavor adjuvants, the nature of theco-ingredient included with the Prins reaction products used informulating the product composition will also serve to alter, modify,augment or enhance the organoleptic characteristics of the ultimatefoodstuff treated therewith.

As used herein in regard to flavors, the terms "alter", "modify" and"augment" in their various forms means "supplying or imparting flavorcharacter or note to otherwise bland, relatively tasteless substances oraugmenting the existing flavor characteristic where a natural flavor isdeficient in some regard or supplementing the existing flavor impressionto modify its quality, character or taste".

The term "enhance" is used herein to mean the intensification of aflavor or aroma charcteristic or note without the modification of thequality thereof. Thus, "enhancement"of a flavor or aroma means that theenhancement agent does not add any additional flavor note.

As used herein, the term "foodstuff" includes both solid and liquidingestible materials which usually do, but need not, have nutritionalvalue. Thus, foodstuffs include soups, convenience foods, beverages,dairy products, candies, chewing gums, vegetables, cereals, soft drinks,snacks and the like.

As used herein, the term "medicinal product" includes both solids andliquids which are ingestible non-toxic materials which have medicinalvalue such as cough syrups, couth drops, aspirin and chewable medicinaltablets.

The term "chewing gum" is intended to mean a composition which comprisesa substantially water-insoluble chewable plastic gum base such aschicle, or substitutes therefor, including jelutong, guttakay rubber orcertain comestible natural or synthetic resins or waxes. Incorporatedwith the gum base in admixture therewith may be plasticizers orsoftening agents, e.g., glycerine; and a flavoring composition whichincorporates the Prins reaction products produced according to theprocess of my invention and, in addition, sweetening agents which may besugars, including sucrose or dextrose and/or artificial sweeteners suchas cyclamates or saccharine. Other optional ingredients may also bepresent.

Substances for use herein as co-ingredients or flavoring adjuvants arewell known in the art for such use, being extensively described in therelevant literature. It is a requirement that any such material be"ingestibly" acceptable and thus non-toxic and otherwise non-deleteriousparticularly from an organoleptic standpoint whereby the ultimate flavorand/or aroma of the consumable material used is not caused to haveunacceptable aroma and taste nuances. Such materials may, in general, becharacterized as flavoring adjuvants or vehicles comprising broadlystabilizers, thickeners, surface active agents, conditioners, otherflavorants and flavor intensifiers.

Stabilizer compounds include preservatives, e.g., sodium chloride;antioxidants, e.g., calcium and sodium ascorbate, ascorbic acid,butylated hydroxy-anisole (mixture of 2- and3-tertiary-butyl-4-hydroxy-anisole), butylated hydroxy toluene(2,6-di-tertiary-butyl-4-methyl phenol), propyl gallate and the like andsequestrants, e.g., citric acid.

Thickener compounds include carriers, binders, protective colloids,suspending agents, emulsifiers and the like, e.g., agar agar,carrageenan; cellulose and cellulose derivatives such as carboxymethylcellulose and methyl cellulose; natural and synthetic gums such as gumarabic, gum tragacanth; gelatin, proteinaceous materials, lipids,carbohydrates; starches, pectins and emulsifiers, e.g., mono- anddiglycerides of fatty acids, skim milk powder, hexoses, pentoses,disaccharides, e.g. sucrose, corn syrup and the like.

Surface active agents include emulsifying agents, e.g., fatty acids suchas capric acid, caprylic acid, palmitic acid, myristic acid and thelike, mono- and diglycerides of fatty acids, lecithin, defoaming andflavor-dispersing agents such as sorbitan monostearate, potassiumstearate, hydrogenated tallow alcohol and the like.

Conditioners include compounds such as bleaching and maturing agents,e.g., benzoyl peroxide, calcium peroxide, hydrogen peroxide and thelike, starch modifiers such as peracetic acid, sodium chlorite, sodiumhypochlorite, propylene oxide, succinic anhydride and the like, buffersand neutralizing agents, e.g., sodium acetate, ammonium bicarbonate,ammonion phosphate, citric acid, lactic acid, vinegar and the like,colorants, e.g. carminic acid, cochineal, tumeric and curcuma and thelike; firming agents such as aluminum sodium sulfate, calcium chlorideand calcium gluconate; texturizers, anti-caking agents, e.g., aluminumcalcium sulfate and tribasic calcium phosphate; enzymes; yeast foods,e.g., calcium lactate and calcium sulfate; nutrient supplements, e.g.,iron salts such as ferric phosphate, gerrous gluconate and the like,riboflavin, vitamins, zinc sources such as zinc chloride, zinc sulfateand the like.

Other flavorants and flavor intensifiers include organic acids, e.g.acetic acid, formic acid, 2-hexenoic acid, benzoic acid, n-butyric acid,caproic acid, caprylic acid, cinnamic acid, isobutyric acid, isovalericacid, alpha-methyl-butyric acid, propionic acid, valeric acid,2-methyl-2-pentenoic acid and 2-methyl-3-pentenoic acid; ketones andaldehydes, e.g. acetaldehyde, acetophenone, acetone, acetyl methylcarbinol, acrolein, n-butanal, crotonal, diacetyl, 2-methyl butanal,β'β-dimethyl acrolein, methyl-n-amyl ketone, n-hexanal, 2-hexenal,isopentanal, hydrocinnanic aldehyde, cis-3-hexenal, 2-heptenal nonylaldehyde, 4-(p-hydroxyphenyl)-2-butanone, alpha-ionone, beta-ionone,methyl-3-butanone, benzaldehyde, β-damascone, β-damascenone,acteophenone, 2-heptanone, o-hydroxyacetophenone,2-methyl-2-hepten-6-one, 2-octanone, 2-undecanone, 3-phenyl-4-pentenal,2-phenyl-2-hexenal, 2-phenyl-2-pentenal, furfural, 5-methyl furfural,cinnamaldehyde, beta-cyclohomocitral, 2-pentanone, 2-pentenal andpropanal; alcohols such as 1-butanol, benzyl alcohol, 1-borneol,trans-2-buten-1-ol, ethanol, geraniol, 1-hexanol, 2-heptanol,trans-2-hexenol-1, cis-3-hexen-1-ol, 3-methyl -3-buten-1-ol, 1-pentanol,1-penten-3-ol, p-hydroxyphenyl-2-ethanol, isoamyl alcohol, isofenchylalcohol, phenyl-2-ethanol, alpha-terpineol, cis-terpineol hydrate,eugenol, linalool, 2-heptanol, acetoin; esters, such as butyl acetate,ethyl acetate, ethyl acetoacetate, ethyl benzoate, ethyl butyrate, ethylcaprate, ethyl caproate, ethyl caprylate, ethyl cinnamate, ethylcrotonate, ethyl formate, ethyl isobutyrate, ethyl isovalerate, ethyllaurate, ethyl myristate, ethyl alpha-methylbutyrate, ethyl propionate,ethyl salicylate, trans-2-hexenyl acetate, n-hexyl acetate, 2-hexenylbutyrate, hexyl butyrate, isoamyl acetate, isopropyl butyrate, methylacetate, methyl butyrate, methyl caproate, methyl isobutyrate,alpha-methylphenylglycidate, ethyl succinate, isobutyl cinnamate,cinnamyl formate, methyl cinnamate and terpenyl acetate; hydrocarbonssuch as dimethyl naphthalene, dodecane, methyl diphenyl, methylnaphthalene, myrcene, naphthalene, octadecane, tetradecane, tetramethylnaphthalene, tridecane, trimethyl naphthalene, undecane, caryophyllene,1-phellandrene, p-cymene, 1-alpha-pinene; pyrazines, such as2,3-dimethylpyrazine, 2,5-dimethylpyrazine, 2,6-dimethylpyrazine,3-ethyl-2,5-dimethylpyrazine, 2-ethyl-3,5,6-trimethylpyrazine,3-isoamyl-2,5-dimethylpyrazine, 5-isoamyl-2,3-dimethylpyrazine,2-isoamyl-3,5,6-trimethylpyrazine, isopropyl dimethylpyrazine, methylethylpyrazine, tetramethylpyrazine, trimethylpyrazine; essential oils,such as jasmine absolute, cassia oil, cinnamon bark oil, rose absolute,orris absolute, lemon essential oil, Bulgarian rose, yara yara andvanilla; lactones, such as δ-nonalactone; sulfides, e.g., methyl sulfideand other materials such as maltol, acetoin and acetals (e.g.,1,1-diethoxyethane, 1,1-dimethoxyethane and dimethoxymethane).

The specific flavoring adjuvant selected for use may be either solid orliquid depending upon the desired physical form of the ultimate product,i.e., foodstuff, whether simulated or natural, ahd should, in any event,(i) be organoleptically compatible with the Prins reaction product(s) ofmy invention by not covering or spoiling the organoleptic properties(aroma and/or taste) thereof; (ii) be non-reactive with one or more ofthe Prins reaction products of my invention and (iii) be capable ofproviding an environment in which the Prins reaction product(s) of myinvention can be dispersed or admixed to provide a homogeneous medium.In addition, selection of one or more flavoring adjuvants, as well asthe quantities thereof will depend upon the precise organolepticcharacter desired in the finished product. Thus, in the case offlavoring compositions, ingredient selection will vary in accordancewith the foodstuff, chewing gum, medicinal product or toothpaste orchewing tobacco to which the flavor and/or aroma are to be imparted,modified, altered or enhanced. In contradistinction, in the preparationof solid products, e.g., simulated foodstuffs, ingredients capable ofproviding normally solid compositions should be selected such as variouscellulose derivatives.

As will be appreciated by those skilled in the art, the amount of Prinsreaction product(s) or derivatives thereof of my invention employed in aparticular instance can vary over a relatively wide range, dependingupon the desired organoleptic effects to be achieved. Thus,correspondingly greater amounts would be necessary in those instanceswherein the ultimate food composition to be flavored (e.g., a"raisin-rum cake") is relatively bland to the taste, whereas relativelyminor quantities may suffice for purposes of enhancing the compositionmerely deficient in natural flavor or aroma, (e.g. when actual raisinsand rum are present in the foodstuff such as the cake). The primaryrequirement is that the amount selected by effective, i.e. sufficient toalter, modify or enhance the orgaloleptic characteristics of the parentcomposition, whether foodstuff per se, chewing gum per se, medicinalproduct per se, toothpaste per se, chewing tobacco per se or flavoringcomposition.

The use of insufficient quantities of one or more Prins reactionproducts or Prins reaction product derivatives of my invention will, ofcourse, substantially vitiate any possibility of obtaining the desiredresults while excess quantities prove needlessly costly and in extremecases, may disrupt the flavoraroma balance, thus proving self-defeating.Accordingly, the terminology "effective amount" and "sufficient amount"is to be accorded a significance in the content of the present inventionconsistent with the obtention of desired flavoring effects.

Thus, and with respect to ultimate food compositions, chewing gumcompositions, medicinal product compositions, chewing tobaccocompositions and toothpaste compositions, it is found that quantities ofone or more Prins reaction products or Prins reaction productderivatives of my invention ranging from a small but effective amount,e.g., about 0.2 parts per million up to about 150 parts per millionbased on total food composition or chewing gum composition, or medicinalproduct composition or toothpaste composition or chewing tobaccocomposition are suitable. Concentrations in excess of the maximumquantity stated are not normally recommended since they fail to providecommensurate enhancement of organoleptic properties. In those instanceswhere one or more Prins reaction products or Prins reaction productderivatives of my invention is added to the foodstuff as an integralcomponent of a flavoring composition, it is, of course, essential thatthe total quantity of flavoring composition employed be sufficient toyield an effective concentration of one or more Prins reaction productsor Prins reaction product derivatives of my invention in the foodstuffproduct.

Food flavoring compositions containing one or more of the compoundsprepared in accordance with the present invention preferably contain oneor more Prins reaction products or Prins reaction product derivatives inconcentrations ranging from about 0.02% up to about 15% by weight of thetotal weight of said flavoring composition.

The compositions described herein can be prepared according toconventional techniques well known as typified by cake batters and fruitdrinks and can be formulated by merely admixing the involved ingredientswithin the proportions stated in a suitable blender to obtain thedesired consistency, homogeneity of dispersion, etc. Alternatively,flavoring compositions in the form of particulate solids can beconveniently prepared by mixing one or more of the Prins reactionproducts or Prins reaction product derivatives prepared in accordancewith my invention with, for example, gum arabic, gum tragacanth, xanthangum, carrageenan and the like, and thereafter spray-drying the resultantmixture whereby to obtain the particulate solid product. Pre-preparedflavor mixes in powder form, e.g. a fruit flavored or rum flavoredpowder mix are obtained by mixing the dried solid components, e.g.,starch, sugar and the like and one or more Prins reaction products orPrins reaction product derivatives of my invention in a dry blenderuntil the requisite degree of uniformity is achieved.

It is presently preferred to combine one or more Prins reaction productderivaties of my invention with at least one of the following adjuvants:

p-Hydroxybenzyl acetone;

Geraniol;

Cassia Oil;

Acetaldehyde;

Maltol;

Ethyl methyl phenyl glycidate;

Benzyl acetate;

Dimethyl sulfide;

Eugenol;

Vanillin;

Caryophyllene;

Methyl cinnamate;

Guiacol;

Ethyl perlargonate;

Cinnamaldehyde;

Methyl Anthranilate;

5-Methyl furfural;

Isoamyl Acetate;

Isobutyl acetate;

Cuminaldehyde;

Alpha ionone;

Cinnamyl formate;

Ethyl butyrate;

Methyl cinnamate;

Acetic acid;

Gamma-undecalactone;

Naphthyl ethyl ether;

Diacetyl;

Furfural;

Ethyl acetate;

Anethole;

2,3-Dimethyl pyrazine;

2-Ethyl-3-methyl pyrazine;

3-Phenyl-4-pentenal;

2-Phenyl-2-hexenal;

2-Phenyl-2-pentenal;

3-Phenyl-4-pentenal diethyl acetal;

β-Damascone (1-crotonyl-2,6,6-trimethylcyclohex-1-ene);

β-Damascenone (1-crotonyl-2,6,6-trimethylcyclohexa-1,3-diene);

Beta-cyclohomocitral (2,6,6-trimethylcyclohex-1-ene carboxaldehyde)

Isoamyl butyrate;

Cis-3-hexenol-1;

2-Methyl-2-pentenoic acid;

Elemecine (4-allyl-1,2,6-trimethoxybenzene);

Isoelmecine (4-propenyl-1,2,6-trimethoxybenzene); and

2-(4-Hydroxy-4-methylpentyl) norbornadiene

rum essence

3-hydroxy butyric acid

2-hydroxy butyric acid

N-methyl anthranilate

cyclotene

ethyl cyclotene

n-propyl cyclotene

gin berry essence

One or more Prins reaction products or Prins reaction productderivatives prepared in accordance with the process of my invention andone or more auxiliary perfume ingredients including, for example,alcohols other than the C₁₁ unsaturated alcohols of my invention,aldehydes, ketones, terpenic hydrocarbons, nitriles, esters other thanthe Prins reaction products of my invention, lactones, natural essentialoils and synthetic essential oils may be admixed so that the combinedodors of the individual components produce a pleasant and desiredfragrance, particularly, and preferably, in rose fragrances. Suchperfume compositions usually contain (a) the main note or the "bouquet"or foundation stone of the composition; (b) modiers which round off andaccompany the main note; (c) fixatives which include odorous substanceswhich lend a particular note to the perfume throughout all states ofevaporation and substances which retard evaporation; and (d) topnoteswhich are usually low-boiling fresh-smelling materials.

In perfume compositions, it is the individual components whichcontribute to their particular olfactory characteristics, however, theoverall sensory effect of the perfume composition will be at least thesum total of the effects of each of the ingredients. Thus, one or morePrins reactions products or Prins reaction product derivatives preparedin accordance with the process of my invention can be used to alter,modify, or enhance the aroma characteristics of a perfume composition,for example, by utilizing or moderating the olfactory reactioncontributed by another ingredient in the composition.

The amount of one or more Prins reaction product or Prins reactionproduct derivative prepared in accordance with the process of myinvention which will be effective in perfume compositions as well as inperfumed articles (e.g. anionic, nonionic, cationic or zwitterionicdetergents, soaps and fabric softener compositions and articles) andcolognes depends upon many factors including the other ingredients,their amounts and the effects which are desired. It has been found thatperfume compositions containing as little as 0.01% of one or more Prinsreaction products or Prins reaction product derivatives prepared inaccordance with the process of my invention and less 50% of one or moreof the Prins reaction products or Prins reaction product derivativesprepared in accordance with the process of my invention or even less(e.g., 0.005%) can be used to impart a woody, ionone-like, fruity,floral, amber, cedarwood-like, vanoris-like, peach, coriander-like,oriental citrusy and minty aroma to soaps, cosmetics, anionic, cationic,nonionic, or zwitterionic detergents, fabric softener compositions,fabric softener articles or other products. The amount employed canrange up to 70% of the fragrance components and will depend onconsiderations of cost, nature of the end product, the effect desired onthe finished product and the particular fragrance sought.

One or more of the Prins reaction products or Prins reaction productderivatives prepared in accordance with the process of my invention isuseful (taken alone or together with other ingredients in perfumecompositions) as (an) olfactory component(s) in detergents and soaps,space odorants and deodorants, perfumes, colognes, toilet water, bathpreparations, such as creams, deodorants, hand lotions and sun screens;powders, such as talcs, dusting powders, face powders and the like. Whenused as (an) olfactory component(s) as little as 0.2% of one or morePrins reaction products or Prins reaction product derivatives preparedin accordance with the process of my invention, will suffice to impartan intense woody, ionone-like, fruity, floral, amber, cedarwood-like,vanoris-like, peach, coriander-like, citrusy and minty aroma tocedarwood formulations. Generally, no more than 6% of one or more of thePrins reaction products or Prins reaction product derivatives of myinvention based on the ultimate end product is required in the perfumedarticle composition.

In addition, the perfume composition or fragrance composition of myinvention can contain a vehicle or carrier for one or more Prinsreaction products or Prins reaction product derivatives prepared inaccordance with the process of my invention. The vehicle can be aliquid, such as a non-toxic alcohol, a non-toxic glycol, or the like,The carrier can also be an absorbent solid, such as a gum (e.g., gumarabic) or components for encapsulating the composition (such asgelatin) as by coacervation.

It will thus be apparent that one or more Prins reaction product orPrins reaction product derivatives prepared in accordance with theprocess of my invention can be utilized to alter, modify or enhancesensory properties, particularly organoleptic properties such as flavorsand/or fragrances of a wide variety of consumable materials.

Furthermore, one or more of the Prins reaction products or derivativesthereof prepared in accordance with the process of my invention arecapable of supplying and/or potentiating certain flavor and aroma notesusually lacking in many smoking tobacco flavors and substitute tobaccoflavors provided herein.

As used herein in regard to smoking tobacco flavors, the terms "alter"and "modify" in their various forms mean "supplying or imparting flavorcharacter or note to otherwise bland smoking tobacco, smoking tobaccosubstitutes, or smoking tobacco flavor formulations or augmenting theexisting flavor characteristic where a natural flavor is deficient insome regard or supplementing the existing flavor impression to modifyits quality, character or taste".

As used herein, the term "enhance" is intended to mean theintensification (without change in kind of quality of aroma or taste) ofone or more taste and/or aroma nuances present in the organolepticimpression of smoking tobacco or a smoking tobacco substitute or asmoking tobacco flavor.

My invention thus provides an organoleptically improved smoking tobaccoproduct and additives therefor, as well as methods of making the samewhich overcome specific problems heretofore encountered in whichspecific desired oriental, fruity, rum-like and Turkish tobacco-likenotes on smoking and prior to smoking in the main stream and in the sidestream are created or enhanced and may be readily controlled andmaintained at the desired uniform level regardless of variations in thetobacco components of the blend.

My invention further provides improved smoking tobacco additives andmethods whereby various oriental, fruity, rum-like and Turkish tobacconotes prior to smoking and on smoking are imparted (in the main streamand in the side stream) to smoking tobacco products and may be readilyvaried and controlled to produce the desired uniform flavorcharacteristics.

In carrying out this aspect of my invention, I add to smoking tobaccomaterials or a suitable substitute therefor (e.g., dried lettuce leaves)an aroma and flavor additive containing as an active ingredient at leastone Prins reaction product or Prins reaction product derivative preparedin accordance with the process of my invention.

In addition to the one or more Prins reaction products or Prins reactionproduct derivatives prepared in accordance with the process of myinvention, other flavoring and aroma additives may be added to thesmoking tobacco materials or substitute therefor either separately or inadmixture with the one or more Prins reaction products or Prins reactionproduct derivatives prepared in accordance with the process of myinvention as follows:

(i) Synthetic Materials

Beta-ethyl-cinnamaldehyde;

Beta-cyclohomocitral;

Eugenol;

Dipentene;

β-Damascenone;

β-Damascone;

Maltol;

Ethyl maltol;

Delta-undecalactone;

Delta-decalactone;

Benzaldehyde;

Amyl acetate;

Ethyl butyrate;

Ethyl valerate;

Ethyl acetate;

2-Hexenol-1;

2-Methyl-5-isopropyl-1,3-nonadiene-8-one;

2,6-Dimethyl-2,6-undecadiene-10-one;

2-Methyl-5-isopropyl acetophenone;

2-Hydroxy-2,5,5,8a-tetramethyl-1-(2-hydroxyethyl)-decahydro-3a,6,6,9a-tetramethylnaphtho[2,1b]-furan;

4-Hydroxy hexanoic acid, gamma lactone; and

Polyisoprenoid hydrocarbons defined in Example V of U.S. Pat. No.3,589,372 issued on June 29, 1971.

(ii) Natural Oils

Celery seed oil;

Coffee extract;

Bergamot Oil;

Cocoa extract;

Nutmeg oil;

Origanum oil;

An aroma and flavoring concentrate containing one or more Prins reactionproducts or Prins reaction product derivatives prepared in accordancewith the process of my invention and, if desired, one or more of theabove-identified additional flavoring additives may be added to thesmoking tobacco material, to the filter or to the leaf or paper wrapper.The smoking tobacco material may be shredded, cured, cased and blendedtobacco material or reconstituted tobacco material or tobaccosubstitutes (e.g., lettuce leaves) or mixtures thereof. The proportionsof flavoring additives may be varied in accordance with taste butinsofar as enhancement or the imparting of natural and/or sweet notes, Ihave found that satisfactory results are obtained if the proportion byweight of the sum total of one or more Prins reaction products or Prinsreaction product derivatives produced to smoking tobacco material isbetween 250 ppm and 1,500 ppm (0.025%-0.15%) of the active ingredientsto the smoking tobacco material. I have further found that satisfactoryresults are obtained if the proportion by weight of the sum total of oneor more Prins reaction products or Prins reaction product derivativesprepared in accordance with the process of my invention is between 2,500and 15,000 ppm (0.25%-1.50%).

Any convenient method for incorporating one or more Prins reactionproducts or Prins reaction product derivatives prepared in accordancewith the process of my invention in the tobacco product may be employed.Thus, one or more Prins reaction products or Prins reaction productderivatives taken alone or along with other flavoring additives may bedissolved in a suitable solvent such as ethanol, pentane, diethyl etherand/or other volatile organic solvents and the resulting solution may beeither sprayed on the cured, cased and blended tobacco material or thetobacco material may be dipped into such solution. Under certaincircumstances, a solution containing one or more Prins reaction productsor Prins reaction product derivatives prepared in accordance with theprocess of my invention taken alone or taken further together with otherflavoring additives as set forth above may be applied by means of asuitable applicator such as a brush or roller on the paper or leafwrapper for the smoking product, or it amy be applied to the filter byeither spraying, or dipping, or coating.

Furthermore, it will be apparent that only a portion of the smokingtobacco or substitute therefor need be treated and the thus treatedtobacco may be blended with other tobaccos before the ultimate tobaccoproduct is formed. In such cases, the tobacco treated may have one ormore Prins reaction products or Prins reaction product derivativesprepared in accordance with the process of my invention in excess of theamount or concentrations above indicated so that when blended with othertobaccos, the final product will have the percentage within theindicated range.

In accordance with one specific example of my invention, an aged, curedand shredded domestic Burley tobacco is sprayed with a 20% ethyl alcoholsolution of substantially pure material produced according to ExampleII, being a mixture of compounds defined according to the structure:##STR83## wherein one of the dashed lines represents a carbon-carbondouble bond and each of the other of the dashed lines representcarbon-carbon single bonds in an amount to provide a tobacco compositioncontaining 800 ppm by weight of said Prins reaction product derivativehaving the structure: ##STR84## on a dry basis.

Thereafter, the alcohol is removed by evaporation and the tobacco ismanufactured into cigarettes by the usual techniques. The cigarette,when treated as indicated, has a desired and pleasing aroma prior tosmoking which can be described as fruity, oriental-like and rum-like andon smoking in the main stream and the side stream, a sweet,oriental-like, fruity, rum-like and Turkish tobacco-like aroma.

While my invention is particularly useful in the manufacture of smokingtobacco such as cigarette tobacco, cigar tobacco and pipe tobacco, othersmoking tobacco products formed from sheeted tobacco dust or fines mayalso be used. Likewise one or more Prins reaction products or Prinsreaction product derivatives prepared in accordance with the process ofmy invention can be incorporated with materials such as filter tipmaterials, seam paste, packaging materials and the like which are usedalong with tobacco to form a product adapted for smoking. Furthermore,one or more of the Prins reaction products or Prins reaction productderivatives prepared in accordance with the process of my invention canbe added to certain tobacco substitutes of natural or synthetic origin(e.g., dried lettuce leaves) and, accordingly, by the term "tobacco" asused throughout this specification is meant any composition intended forhuman consumption by smoking or otherwise, whether composed of tobaccoplant parts or substitute materials or both.

The following Example A sets forth means for synthesizing precursors foruse in synthesizing the products of my invention. The following ExamplesI-V illustrate methods of my invention used to manufacture Prinsreaction products and Prins reaction product derivatives of myinvention. Examples subsequent to Example V serve to illustrate theorganoleptic utilities of my invention of the Prins reaction productsand Prins reaction product derivatives manufactured in accordance withthe processes of Examples I-V.

All parts and percentages given herein are by weight unless otherwisespecified.

EXAMPLE A Preparation of Diisoamylenes

Reaction: ##STR85##

Diisoamylene is prepared according to one of the procedures set forth inthe following references:

(i) Murphy & Lane, Ind. Eng. Chem., Prod. Res. Dev., Vol. 14, No. 3,1975 p. 167 (Title: Oligomerization of 2-Methyl-2-Butene in SulfuricAcid and Sulfuric-Phosphoric Acid Mixtures).

(ii) Whitmore & Mosher, Vol. 68, J. Am. Chem. Soc., February, 1946, p.281 (Title: The Depolymerization of 3,4,5,5-Tetramethyl-2-hexene and3,5,5,-Trimethyl-2-heptene in Relation to the Dimerization ofIsoamylenes).

(iii) Whitmore & Stahly, Vol. 67, J. Am. Chem. Soc., December, 1945, p.2158 (Title: The Polymerization of Olefins. VIII The Polymerization ofOlefins in Relation to Intramolecular Rearrangements. II).

(iv) U.S. Pat. No. 3,627,700 issued on Dec. 14, 1971, (Zuech).

(v) U.S. Pat. No. 3,538,181 issued on Nov. 3, 1970, (Banks).

(vi) U.S. Pat. No. 3,461,184 issued on Aug. 12, 1969 (Hay, et al).

(vii) Gurwitsch, Chemische Berichte, 1912, Vol. 2, p. 796 (Production ofDi-isoamylene From Isoamylene Using Mercury Acetate Catalyst).

As an illustration, and not by way of limitation, the following examplesets forth the preparation of diisoamylenes useful in producing thefragrance materials of my invention.

Over a period of ten hours, 2-methyl-2-butene is pumped through a 5'×5/8(0.625 inch) tube packed with 15.0 grams of polystyrene sulfonic acidcatalyst, at a temperature of 100° C. and at a pressure of 400 psig.

The resulting material was distilled in a fractionation column in orderto separate the diisoamylene from the higher molecular weight polymers,which are formed during the reaction as by-products.

FIG. AA represents the GLC profile for the reaction product of thisExample A using a 70% sulfuric acid catalyst at 35° C.

FIG. AB represents the GLC profile for the reaction product of thisExample A using an Amberlyst® 15 acidic ion exchange resin catalyst at atemperature of 150° C.

FIG. AC represents the GLC profile for the reaction product of thisExample A, using an Amberlyst® 15 catalyst at 100° C.

FIG. AD represents the GLC profile for the reaction product of thisExample A, using a sulfuric acid catalyst and an alpha-methylstyrenediluent at 35° C. according to the conditions of United Kingdom PatentSpecification No. 796,130 (crude reaction product).

FIG. AE represents the GLC profile for the reaction product of thisExample A, using a sulfuric acid catalyst at 35° C. and analpha-methylstyrene diluent according to the conditions of UnitedKingdom Patent Specification 796,130 (distilled reaction product).

FIG. BA represents the NMR spectrum for peak 1 of the GLC profile ofFIG. AE. Peak 1 has been determined by analysis to be the compoundhaving the structure: ##STR86##

FIG. BB represents the infra-red spectrum for peak 1 of the GLC profileof FIG. AE.

FIG. CA represents the NMR spectrum for peak 2 of the GLC profile ofFIG. AE. Peak 2 contains the compounds having the structures: ##STR87##

FIG. CB represents the infra-red spectrum for peak 2 of the GLC profileof FIG. AE.

FIG. D represents the NMR spectrum for peak 2 of the GLC profile of FIG.AB.

EXAMPLE I Preparation of Acetic Acid Ester Mixture of C₁₁ Alcohols

Reaction: ##STR88##

Into a 3 liter reaction flask equipped with reflux condenser, additionfunnel, thermometer, stirrer and heating mantle is placed 1428 ml aceticanhydride (14 moles) and 25 ml boron trifluoride etherate (0.25 moles).The reaction mass is heated to 103° C. and while maintaining thereaction mass at 103°-108° C., over a period of 30 minutes, a mixture of1600 ml diisoamylene prepared according to Example A (10.6 moles) and324 grams of paraformaldehyde (10.8 moles of formaldehyde) is addedslowly to the reaction mass. The reaction mass is then maintained at85°-88° C. over a period of 2 hours. The reaction mass is then cooledand poured onto 2 liters of water and washed with 3 two-liter volumes of5% sodium hydroxide followed by one 1500 ml portion of saturated sodiumchloride. The reaction mass is then mixed with 400 ml methylenedichloride and dried over anhydrous sodium sulfate. The reaction mass isthen distilled on a 2 inch packed column yielding the followingfractions:

    ______________________________________                                        Fraction                                                                             Vapor      Liquid     Pressure                                                                             Weight of                                 Number Temp. (°C.)                                                                       Temp. (°C.)                                                                       mm/Hg. Fraction (g)                              ______________________________________                                        1      36          73        1.4     92                                       2      73          90        .6      96                                       3      82          99        .6     106                                       4      86         102        .6     105                                       5      86         105               110                                       6      95         146        1.5    218                                       7      146        224                68                                       ______________________________________                                    

and then redistilled on a 6 inch silver column packed with stones toyield the following fractions:

    ______________________________________                                        Fraction                                                                             Vapor      Liquid     Pressure                                                                             Weight of                                 Number Temp. (°C.)                                                                       Temp. (°C.)                                                                       mm/Hg. Fraction (g)                              ______________________________________                                        1      30/89      89/96      4.4/4.4                                                                              34                                        2      78         93         2.0    93.5                                      3      94         75         2.0    84                                        4      77         95         1.6    75.7                                      5      80         97         1.6    93.8                                      6      80         100        1.6    90                                        7      81         104        1.6    75                                        8      84         115        1.6    45.3                                      9      138        181        1.6    50.8                                      ______________________________________                                    

FIG. 1 is the GLC profile for the reaction product prior todistillation.

FIG. 2 is the GLC profile for fraction 8 of the foregoing distillationproduct of the foregoing reaction product.

FIG. 3 is the NMR spectrum for the foregoing reaction product subsequentto distillation.

FIG. 4 is the infra-red spectrum for the foregoing reaction product.

EXAMPLE II Preparation of C₁₁ Alcohol

Reaction: ##STR89##

Into a 5 liter reaction flsk equipped with stirrer, addition funnel,thermometer, nitrogen purge apparatus and heating mantle is placed:

1155 grams of the ester mixture prepared according to Example I

864 grams of 50% sodium hydroxide solution (10.8 moles)

1 liter water

The reaction mass is heated at reflux with stirring for a period of 12hours at 65°-67° C.

The reaction mass is then transferred to an open head separatory funneland washed with one liter of saturated sodium chloride solutionwhereupon the pH of the oil layer is 6 and the pH of the aqueous layeris 12. The net weight of the oil layer is 1192 grams. The reaction massis then distilled on a 2 inch stone packed column yielding the followingfractions:

    ______________________________________                                        Fraction                                                                             Vapor      Liquid     Pressure                                                                             Weight of                                 Number Temp. (°C.)                                                                       Temp. (°C.)                                                                       mm/Hg. Fraction (g)                              ______________________________________                                        1      52/85      80/90      182/125                                                                              75                                        2      55         105        110    94                                        3      78         106        30     76                                        4      88         106        1      84                                        5      81         89         1      92                                        6      83         73         1      94                                        7      71         81         1      79                                        8      69         80         1      83                                        9      69         80         1      80                                        10     69         80         1      86                                        11     68         82         1      87                                        12     69         82         1      90                                        13     66         90         1                                                14     60         125        1                                                ______________________________________                                    

FIG. 5 is the GLC profile for the resulting reaction product.

FIG. 6 is the NMR spectrum for fraction 7 of the foregoing distillationof the instant reaction product.

FIG. 7 is the infra-red spectrum for the foregoing reaction product.

EXAMPLE III Formation of C₁₁ Unsaturated Alcohol Propionate

Reaction: ##STR90## wherein in each of the compounds, one of the dashedlines represents a carbon-carbon double bond and each of the other ofthe dashed lines represent carbon-carbon single bonds.

Into a 1 liter reaction flask equipped with reflux condenser, additionfunnel, thermometer, heating mantle and nitrogen feed line, is placed400 ml (3.0 moles) of propionic anhydride. The propionic anhydride isheated to 110° C. and through the addition funnel is added 225 grams(1.5 moles) of the alcohol produced according to Example II. Thereaction mass is maintained at 100° C. for a period of a half hourduring the addition. At the completion of the addition (after a halfhour), 20 ml of 50% sodium hydroxide and 80 ml water is added to thereaction mass. The reaction mass is stirred for an additional half hourat 110° C.

The reaction mass is transferred to an open head separatory flaskcontaining 2 liters of water. Two phases now exist; an aqueous phase andan organic phase. The organic phase is washed with 100 ml 5% sodiumhydroxide. The oil phase is then washed with 100 ml saturated sodiumchloride solution so that the pH is 6. The reaction mass is thendistilled on a 1 inch stone packed column yielding the followingfractions:

    ______________________________________                                        Fraction                                                                             Vapor      Liquid     Pressure                                                                             Weight of                                 Number Temp. (°C.)                                                                       Temp. (°C.)                                                                       mm/Hg. Fraction (g)                              ______________________________________                                        1      49/169     95/120     78     43                                        2      98         106        1      55                                        3      90         100        1      46                                        4      85          98        1      45                                        5      83          89        1      47                                        6      84          99        1      56                                        7      84          99        1      50                                        8      66         143        1      40                                        9      55         170        1                                                ______________________________________                                    

FIG. 8 is the GLC profile of the reaction product.

FIG. 9 is the NMR spectrum for the reaction product.

FIG. 10 is the infra-red spectrum of the reaction product.

EXAMPLE IV Preparation of Isobutyric Acid Ester of C₁₁ Alcohol

Reaction ##STR91##

Into a 1 liter reaction flask equipped with reflux condenser, additionfunnel, thermometer, heating mantle, gas bubbler and nitrogen purgeapparatus, is placed 475 grams of isobutyric anhydride. The isobutyricanhydride is heated to 110° C. with stirring. Over a period of 1.5hours, the C₁₁ alcohol mixture produced according to Example II, 255grams, is added to the propionic anhydride. At the end of the additionof the C₁₁ alcohol, the reaction mass is heated for another 30 minutesat 110° C. The reaction mass is then admixed with 20 ml 50% sodiumhydroxide and 80 ml water. The reaction mass is then transferred to aseparatory funnel containing 1 liter of water. The reaction massseparates into an organic phase and an aqueous phase. The organic phaseis washed with two 200 ml portions of water and stirred for 15 minutes.The organic phase is then washed with 5% sodium hydroxide until a pH of6.

The reaction mass is then distilled on a 2 inch stone packed columnyielding the following fractions:

    ______________________________________                                        Fraction                                                                             Vapor      Liquid     Pressure                                                                             Weight of                                 Number Temp. (°C.)                                                                       Temp. (°C.)                                                                       mm/Hg. Fraction (g)                              ______________________________________                                        1      34/42      55/68      .1     76                                        2      69         91         .1     77                                        3      80         95         .1     88                                        4      69         90         .1     90                                        5      67         113        .1     75                                        6      68         165        .1     12                                        ______________________________________                                    

FIG. 11 is the GLC profile for bulked fractions 1-6 of the foregoingreaction product.

FIG. 12 is the NMR spectrum for the major peak in the GLC profile ofFIG. 11 which consists of the compound having the structure: ##STR92##

FIG. 13 is the infra-red spectrum for the major component of the GLCprofile of FIG. 11 produced according to this example consisting of thecompound having the structure: ##STR93##

EXAMPLE V(A) Production of Reaction Product of Diisomylene withFormaldehyde and Acetic Anhydride in the Presence of Sulfuric AcidCatalyst

Reaction: ##STR94##

Into a 12 liter, 3 neck reaction flask equipped with stirrer,thermometer, reflux condenser and addition funnel, is placed 3,400 mlglacial acetic acid; 1,040 grams acetic anhydride followed by 1,200grams of paraformaldehyde (powder) and 40 grams of concentrated (93%)sulfuric acid. The resulting mixture is heated to 90° C. Dropwise, overa period of 2 hours while maintaining the reaction temperature at 90°C., 2,800 grams (4 liters) of diisoamylene prepared according to ExampleA is added to the reaction mass. The reaction mass is then stirred foran additional 1 hour at 90° C.

The reaction mass is then cooled to room temperature and poured into 2liters of water. The organic layer is separated from the resultantaqueous layer and the organic layer is washed as follows:

One 1 liter portion of water

Two liters of 12.5% sodium hydroxide solution

Two 1 liter portions of saturated sodium chloride solution

The resulting organic layer is then dried over anhydrous magnesiumsulfate, filtered, and stripped of solvent.

The resulting concentrate is then fractionally distilled on a 2 inchstone packed column yielding the following distillation fractions and atthe following conditions:

    ______________________________________                                        Fraction                                                                             Vapor      Liquid     Pressure                                                                             Weight of                                 Number Temp. (°C.)                                                                       Temp. (°C.)                                                                       mm/Hg. Fraction (g)                              ______________________________________                                        1      32/45      52/59      3.0/2.0                                                                              330                                       2      62          75        2.0    352                                       3                                   377                                       4      81          95        2.0    405                                       5      90         105        2.0    398                                       6      95         111        2.0    404                                       7      101        120        2.0    369                                       ______________________________________                                    

The resulting product is then redistilled (bulked fractions 2,3,4,5,6and 7) on a Goodloe yielding the following fractions:

    ______________________________________                                        Fraction                                                                             Vapor      Liquid     Pressure                                                                             Weight of                                 Number Temp. (°C.)                                                                       Temp. (°C.)                                                                       mm/Hg. Fraction (g)                              ______________________________________                                         1     43/67      97/90      6      78                                         2     73         93         6      73                                         3     76         93         6      45                                         4     76         93         6      79                                         5     81         95         6      33                                         6     82         95         6      91                                         7     81         95         6      101                                        8     81         95         6      78                                         9     65         92         3      79                                        10     65         92         3      75                                        11     63         92         3      86                                        12     63         93         3      97                                        13     63         93         3      97                                        14     63         94         3      97                                        15     63         97         3      108                                       16     63         98         3      78                                        17     63         101        3      94                                        18     66         104        3      44                                        19     68         108        3      64                                        20     69         115        3      70                                        21     74         130        3      52                                        22     85         135        3      71                                        23     100        136        3      58                                        24     110        147        3      97                                        25     118        225        3      66                                        ______________________________________                                    

FIG. 14 is the GLC profile for fraction 2 of the foregoing distillationof the reaction product of this example.

FIG. 15 is the GLC profile for fraction 9 of the foregoing distillationproduct of the reaction product of this example.

FIG. 16 is the NMR spectrum for the reaction product of this example.

FIG. 17 is the infra-red spectrum for peak 2 of FIG. 14, the GLC profilefor fraction 2 of the foregoing distillation product of the reactionproduct of this example.

EXAMPLE V(B) Hydrolysis of Cyclic Material Prepared According to ExampleV(A)

Reaction: ##STR95##

Into a 5 liter reaction flask equipped with thermometer, stirrer andreflux condenser is charged:

1,400 grams of the cyclic ether prepared according to Example V(A)

1,046 grams of 50% aqueous sodium hydroxide

100 ml water

5 grams of Aliquat® 336 (cetyl trimethyl ammonium chloride manufacturedby the General Mills Chemical Company of Minneapolis, Minn.)

The reaction mass is heated to reflux and maintained at reflux for aperiod of 8 hours (111° C.; atmospheric pressure). The reaction mass issubsequently cooled to room temperature and is now in two phases, anaqueous phase and an organic phase. The organic phase is removed andwashed with saturated sodium chloride whereby the pH thereof is 7-8.

The crude oil is then removed and distilled on an 18 inch Goodloe,silver mirror distillation column yielding the following fractions:

    ______________________________________                                               Vapor    Liquid                Weight of                               Fraction                                                                             Temp.    Temp.   Pressure                                                                              Reflux                                                                              Fraction                                Number (°C.)                                                                           (°C.)                                                                          mm/Hg.  Ratio (g)                                     ______________________________________                                        1      88/89    60/60     4/2.4 4:1   68                                      2      60       90      2.4     4:1   97                                      3      60       90      2.4     4:1   93                                      4      60       90      2.0     4:1   85                                      5      53/58    89/90   1.7/1.4 4:1   88                                      6      58       91      1.2           89                                      7      60       90      1.6     4:1   95                                      8      58       93      1.3     4:1   95                                      9      63       95      1.4     1:1   85                                      10     63       99      1.3     1:1   102                                     11     63       102     1.2     1:1   88                                      12     65       104     1.2     1:1   89                                      13     68       115     1.2     1:1   86                                      14     68       220     1.2     1:1   54                                      ______________________________________                                    

The resulting material is then analyzed via IR, NMR and mass spectralanalysis. The infra-red spectrum is set forth in FIG. 18.

EXAMPLE VI

The following Chypre formulation is prepared:

    ______________________________________                                        Musk ambrette             40                                                  Musk ketone               60                                                  Coumarin                  30                                                  Oil of bergamot           150                                                 Oil of lemon              100                                                 Methyl ionone             50                                                  Hexyl cinnamic aldehyde   100                                                 Hydroxycitronellal        100                                                 Oil of lavender           50                                                  Texas cedarwood oil       85                                                  Virginia cedarwood oil    30                                                  Oil of sandalwood         40                                                  (East Indies)                                                                 Isoeugenol                20                                                  Eugenol                   10                                                  Benzyl acetate            30                                                  β-phenyl ethyl alcohol                                                                             40                                                  α-phenyl ethyl alcohol                                                                            30                                                  Oakmoss absolute          30                                                  Vetiver oil Venezuela     25                                                  C.sub.11 unsaturated alcohol                                                                            25                                                  acetate product of Example I                                                  defined according to the                                                      structure:                                                                     ##STR96##                                                                    wherein one of the dashed                                                     lines in each of the molecules                                                of the mixture is a carbon-                                                   carbon double bond and each of                                                the other of the dashed lines                                                 represent carbon-carbon single                                                bonds                                                                         ______________________________________                                    

The C₁₁ unsaturated alcohol acetate ester prepared according to ExampleII imparts to the Chypre formulation an intense, woody, ionone-like,fruity and floral aroma with oriental-type undertones. The Chypreformulation with the additional intense nuances caused by the use of theproduct of Example II is advantageously and unexpected in the perfumeindustry.

EXAMPLE VII Chypre Formulation

The following chypre formulation is prepared:

    ______________________________________                                        Musk ambrette        40                                                       Musk ketone          60                                                       Coumarin             50                                                       Oil of bergamot      150                                                      Oil of lemon         100                                                      Methyl ionone        10                                                       Hexyl cinnamic aldehyde                                                                            150                                                      Hydroxycitronnellal  100                                                      Oil of lavender      50                                                       Sandalwood oil Guyana                                                                              120                                                      Isoeugenol           20                                                       Oil of vetiver Venezuela                                                                           320                                                      Texas cedarwood oil  25                                                       C.sub.11 unsaturated alcohol                                                                       85                                                       propionic acid ester prepared                                                 according to Example III                                                      ______________________________________                                    

The use of the C₁₁ unsaturated alcohol propionic acid ester preparedaccording to Example III containing the compounds defined according tothe structure: ##STR97## wherein one of the dashed lines is acarbon-carbon double bond in each of the molecules and each of the otherof the dashed lines represents carbon-carbon single bonds causes thischypre formulation to have a fruity, floral, woody, cedarwood-like aromaprofile with amber undertones and oriental topnotes. This interstingchypre nuance is novel in the perfumery industry and has unexpected,unobvious and advantageous properties.

EXAMPLE VIII Pine Fragrance

The following pine fragrance formulation is produced:

    ______________________________________                                        Ingredients            Parts by Weight                                        ______________________________________                                        Isobornyl acetate      100                                                    Camphor                10                                                     Terpeineol             25                                                     Fir balsam absolute    20                                                     (50% in diethyl phthalate)                                                    Coumarin               4                                                      Linalool               30                                                     Fenchyl alcohol        10                                                     Anethol                12                                                     Lemon terpenes washed  50                                                     Borneol                5                                                      Galbanum oil           5                                                      Turpentine Russian     150                                                    Eucalyptol             50                                                     2,2,6-trimethyl-1-cyclohexene-                                                                       12                                                     1-carboxaldehyde                                                              Maltol (1% in diethyl phthalate)                                                                     5                                                      Isobutyric acid ester of C.sub.11 unsaturated                                                        28                                                     alcohol prepared according to Example                                         IV containing a mixture of compounds                                          defined according to the structure:                                            ##STR98##                                                                    wherein in each of the molecules of the                                       mixture, one of the dashed lines is a                                         carbon-carbon double bond and each of                                         the other of the dashed lines                                                 represent carbon-carbon single bonds                                          ______________________________________                                    

The isobutryl ester of the C₁₁ unsaturated alcohol prepared according toExample IV imparts to this pine fragrance a fruity, vanoris-like, peach,coriander-like, cedarwood-like and oriental-like aroma profile.

EXAMPLE IX Citrus Cologne Formulation

The following citrus cologne formultion is prepared:

    ______________________________________                                        Ingredients          Parts by Weight                                          ______________________________________                                        Cyclic ether having the structure:                                                                 600                                                       ##STR99##                                                                    prepared according to Example V                                               wherein in the mixture in each                                                of the molecules, one of the                                                  dashed lines represents a                                                     carbon-carbon double bond and                                                 the other of the dashed lines                                                 represent carbon-carbon single                                                bonds                                                                         Bergamot oil         100                                                      Phenyl ethyl alcohol 100                                                      Hydroxy citronellal  100                                                      Benzyl salicylate    100                                                      ______________________________________                                    

The use of the cyclic ether mixture produced according to Example V,defined according to the structure: ##STR100## imparts to this citruscologne formulation a woody, ionone-like, oriental and minty aromaprofile in addition to the strong citrus aroma.

EXAMPLE X Preparation of Cosmetic Powder Compositions

Cosmetic poweder compositions are prepared by mixing in a ball mill 100grams of talcum powder with 0.25 grams of each of the substances setforth in Table II below. Each of the cosmetic powder compositions has anexcellent aroma as described in Table II below:

                  TABLE II                                                        ______________________________________                                        Substance          Aroma Description                                          ______________________________________                                        Mixture of substances prepared                                                                   A woody, ionone-like,                                      according to Example I and                                                                       fruity and floral aroma                                    defined according to the                                                                         with oriental-like topnotes                                structure:         and undertones.                                            wherein in each of the molecules                                              of the mixture, one of the                                                    dashed lines reperesents a carbon-                                            carbon double bond and each of                                                the other of the dashed lines                                                 represent carbon-carbon single                                                bonds.                                                                        Mixture of compounds prepared                                                                    A woody, amber and floral                                  according to Example II containing                                                               aroma profile with minty and                               compounds defined according to                                                                   oriental undertones.                                       the generic structure:                                                         ##STR102##                                                                   wherein in each of the molecules                                              of the mixture, one of the                                                    dashed lines represents a carbon-                                             carbon double bond and each of                                                the other of the dashed lines -represent carbon-carbon single                 bonds.                                                                        Mixture of compounds prepared                                                                    A fruity, floral, woody                                    according to Example III con-                                                                    and cedarwood aroma                                        taining compounds defined                                                                        profile with amber and                                     according to the generic                                                                         oriental-like topnotes.                                    structure:                                                                     ##STR103##                                                                   wherein in each of the molecules                                              of the mixture, one of the                                                    dashed lines represents a                                                     carbon-carbon double bond and                                                 each of the other of the dashed                                               lines reperesent carbon-carbon                                                single bonds.                                                                 Mixture of compounds prepared                                                                    A fruity, vanoris-like,                                    according to Example IV defined                                                                  peach, coriander, cedar-                                   according to the generic                                                                         wood-like and oriental                                     structure:         aroma profile.                                              ##STR104##                                                                   wherein in each of the molecules                                              of the mixture, one of the                                                    dashed lines represents a                                                     carbon-carbon double bond and                                                 each of the other of the dashed                                               lines represent carbon-carbon                                                 single bonds.                                                                 Mixture of compounds produced                                                                    A woody, ionone-like,                                      according to Example V(A) defined                                                                oriental, citrusy aroma                                    according to the generic                                                                         with minty topnotes.                                       structure:                                                                     ##STR105##                                                                   wherein in each of the molecules                                              of the mixture, one of the dashed                                             lines is a carbon-carbon double                                               bond and each of the other of                                                 the dashed lines represent carbon-                                            carbon single bonds.                                                          Perfume composition produced                                                                     A chypre-type aroma with                                   according to Example VI.                                                                         woody, ionone-like, fruity,                                                   floral and oriental-like                                                      topnotes.                                                  Perfume composition prepared                                                                     A chypre aroma with fruity,                                according to Example VII.                                                                        floral, woody, cedarwood,                                                     amber and oriental-like                                                       undertones.                                                Perfume composition prepared                                                                     A pine aroma with fruity,                                  according to Example VIII.                                                                       vanoris-like, peach,                                                          coriander-like, cedarwood                                                     and oriental topnotes.                                     Perfume composition prepared                                                                     A citrus aroma with woody,                                 according to Example IX.                                                                         ionone-like, oriental,                                                        and minty undertones.                                      ______________________________________                                    

EXAMPLE XI Perfumed Liquid Detergents

Concentrated liquid detergents (Lysine sale of n-dodecylbenzene sulfonicacid as more specifically described in U.S. Pat. No. 3,948,818, issuedon Apr. 16, 1976) with aroma nuances as set forth in Table II of ExampleX, are prepared containing 0.10%, 0.15%, 0.20%, 0.25%, 0.30% and 0.35%of the substance set forth in Table II of Example X. They are preparedby adding and homogeneously mixing the appropriate quantity of substanceset forth in Table II of Example X below in the liquid detergent. Thedetergents all possess excellent aromas as set forth in Table II ofExample X, the intensity increasing with greater concentrations ofsubstance as set forth in Table II of Example X.

EXAMPLE XII

Preparation of Colognes and Handkerchief Perfumes

Compositions as set forth in Table II of Example X are incorporated intocolognes at concentrations of 2.0%, 2.5%, 3.0%, 3.5%, 4.0%, 4.5% and5.0% in 80%, 85%, 90% and 95% aqueous food grade ethanol solutions; andinto handkerchief perfumes at concentrations of 15%, 20%, 25% and 30%(in 80%, 85%, 90% and 95% aqueous food grade ethanol solutions).Distinctive and definitive fragrances as set forth in Table II ofExample X are imparted to the colognes and to the handkerchief perfumesat all levels indicated.

EXAMPLE XIII Preparation of Soap Compositions

One hundred grams of soap chips [per sample] (IVORY®, produced by theProcter & Gamble Company of Cincinnati, Ohio), are each mixed with onegram samples of substances as set forth in Table II of Example X untilhomogeneous compositions are obtained. In each of the cases, thehomogeneous compositions are heated under 8 atmospheres pressure at 180°C. for a period of three hours and the resulting liquids are placed intosoap molds. The resulting soap cakes, on cooling, manifest aromas as setforth in Table II of Example X.

EXAMPLE XIV Preparation of Solid Detergents Compositions

Detergents are prepared using the following ingredients according toExample I of Canadian Pat. No. 1,007,948:

    ______________________________________                                        Ingredient        Percent by Weight                                           ______________________________________                                        Neodol ® 45-11 (a C.sub.14 -C.sub.15                                                        12                                                          alcohol ethoxylated with                                                      11 moles of ethylene oxide)                                                   Sodium carbonate  55                                                          Sodium citrate    20                                                          Sodium sulfate, water                                                                           q.s.                                                        brighteners                                                                   ______________________________________                                    

This detergent is a phosphate-free detergent. Samples of 100 grams eachof this detergent are admixed with 0.10, 0.15, 0.20 and 0.25 grams ofeach of the substances as set forth in Table II of Example X. Each ofthe detergent samples has an excellent aroma as indicated in Table II ofExample X.

EXAMPLE XV

Utilizing the procedure of Example I at column 15 of U.S. Pat. No.3,632,396, nonwoven cloth substrates useful as dry-added fabricsoftening articles of manufacture are prepared wherein the substrate,the substrate coating and the outer coating and the perfuming materialare as follows:

1. A water "dissolvable" paper ("Dissolve Paper")

2. Adogen 448 (m.p. about 140° F.) as the substrate coating; and

3. An outer coating having the following formulation (m.p. about 150°F.):

57% C₂₀₋₂₂ HAPS

22% isopropyl alcohol

20% antistatic agent

1% of one of the substances as set forth in Table II of Example X

Fabric softening compositions prepared according to Example I at column15 of U.S. Pat. No. 3,632,396 having aroma characteristics as set forthin Table II of Example X, consist of a substrate coating having a weightof about 3 grams per 100 square inches of substrate; a first coating onthe substrate coating consisting of about 1.85 grams per 100 squareinches of substrate; and an outer coating coated on the first coatingconsisting of about 1.4 grams per 100 square inches of substrate. One ofthe substances of Table II of Example X is admixed in each case with theouter coating mixture, thereby providing a total aromatized outercoating weight ratio to substrate of about 0.5:1 by weight of thesubstrate. The aroma characteristics are imparted in a pleasant mannerto the head space in a dryer on operation thereof in each case usingsaid dry-added fabric softener non-woven fabrics and these aromacharacteristics are described in Table II of Example X.

EXAMPLE XVI Hair Spray Formulations

The following hair spray formulation is prepared by first dissolvingPVP/VA E-735 copolymer manufactured by the GAF Corporation of 140 West51st Street, New York, N.Y., in 91.62 grams of 95% food grade ethanol.8.0 grams of the polymer is dissolved in the alcohol. The followingingredients are added to the PVP/VA alcoholic solution:

    ______________________________________                                        Dioctyl sebacate     0.05 weight percent                                      Benzyl alcohol       0.10 weight percent                                      Dow Corning 473 fluid                                                                              0.10 weight percent                                      (prepared by the Dow Corning                                                  Corporation)                                                                  Tween 20 surfactant  0.03 weight percent                                      (prepared by ICI America                                                      Corporation)                                                                  One of the perfumery substances                                                                    0.10 weight percent                                      as set forth in Table II of                                                   Example X                                                                     ______________________________________                                    

The perfuming substances as set forth in Table II of Example X add aromacharacteristics as set forth in Table II of Example X which are ratherintense and aesthetically pleasing to the users of the soft-feel,good-hold pump hair sprays.

EXAMPLE XVII Conditioning Shampoos

Monamid CMA (prepared by the Mona Industries Company) (3.0 weightpercent) is melted with 2.0 weight percent coconut fatty acid (preparedby Procter & Gamble Company of Cincinnati, Ohio); 1.0 weight percentethylene glycol distearate (prepared by the Armak Corporation) andtriethanolamine (a product of Union Carbide Corporation) (1.4 weightpercent). The resulting melt is admixed with Stepanol WAT produced bythe Stepan Chemical Company (35.0 weight percent). The resulting mixtureis heated to 60° C. and mixed until a clear solution is obtained (at 60°C.).

Gafquat® 755 N polymer (manufactured by GAF Corporation of 140 West 51stStreet, New York, N.Y.) (5.0 weight percent) is admixed with 0.1 weightpercent sodium sulfite and 1.4 weight percent polyethyelene glycol 6000distearate produced by Armak Corporation.

The resulting material is then mixed and cooled to 45° C. and 0.3 weightpercent of perfuming substance as set forth in Table II of Example X isadded to the mixture. The resulting mixture is cooled to 40° C. andblending is carried out for an additional one hour in each case. At theend of this blending period, the resulting material has a pleasantfragrance as indicated in Table II of Example X.

EXAMPLE XVIII Tobacco Formulations

Tobacco mixtures are prepared by admixing the following ingredients:

    ______________________________________                                        Ingredients     Parts by Weight                                               ______________________________________                                        Bright          40.1                                                          Burley          24.9                                                          Maryland        1.1                                                           Turkish         11.6                                                          Stem (flue-cured)                                                                             14.2                                                          Glycerine       2.8                                                           Water           5.3                                                           ______________________________________                                    

Cigarettes are prepared from this tobacco.

The following flavor formulation is prepared:

    ______________________________________                                        Ingredients    Parts by Weight                                                ______________________________________                                        Ethyl butyrate .05                                                            Ethyl valerate .05                                                            Maltol         2.00                                                           Cocoa extract  26.00                                                          Coffee extract 10.00                                                          Ethyl alcohol  20.00                                                          Water          41.90                                                          ______________________________________                                    

The above stated tobacco flavor formulation is applied at the rate of1.0% to all of the cigarettes produced using the above tobaccoformulation. The cigarettes are divided into groups as follows:

Group A treated with 500 ppm of a mixture of compounds defined accordingto the structure: ##STR106## prepared according to Example I wherein inthe mixture each of the molecules contains a compound wherein one of thedashed lines is a carbon-carbon double bond and each of the other of thedashed lines represents a carbon-carbon single bond.

Group B--a mixture of compounds defined according to the structure:##STR107## produced according to Example II wherein in the mixture ineach of the molecules, one of the dashed lines represents acarbon-carbon double bond and each of the other of the dashed linesrepresent carbon-carbon single bonds.

Group C--mixture of compounds defined according to the structure:##STR108## produced according to Example III wherein in each ofmolecules, one of the dashed lines represents a carbon-carbon doublebond and each of the other of the dashed lines represent carbon-carbonsingle bonds.

Group D--a mixture of compounds defined according to the genus:##STR109## produced according to Example IV wherein in each of themolecules, one of the dashed lines represents a carbon-carbon doublebond and each of the other of the dashed lines represent carbon-carbonsingle bonds.

Group E--a mixture of compounds defined according to the genus:##STR110## wherein in the mixture in each of the molecules, one of thedashed lines represents a carbon-carbon double bond and each of theother of the dashed lines represent carbon-carbon single bonds.

Group F--not treated with any additional substances.

Group F is indicated to be "control cigarettes". The control cigarettesand the experimental cigarettes, Groups A, B, C, D and E, which containvarious compounds defined according to the genus: ##STR111## wherein oneof the dashed lines represents a carbon-carbon double bond and each ofthe other of the dashed lines represent carbon-carbon single bonds;wherein the wavy line represents a carbon-carbon single bond or no bond;wherein when the wavy line represents a carbon-carbon single bond, Zrepresents methylene and when the wavy line represents no bond, Zrepresents hydrogen or C₂ -C₄ acyl prepared according to Examples I-V(B)inclusive, are evaluated by paired comparison and the results are asfollows:

The experimental cigarettes of Groups A, B, C, D and E are found to havemore body and tobacco smoke flavor and a fuller body sensation. Thetobacco notes are described as "Turkish-like" with oriental, fruity andrum-like nuances both prior to and on smoking in the main stream and inthe side stream. The flavor of the tobacco on smoking is in addition,sweeter and more aromatic. All of the cigarettes are evaluated for smokeflavor with a 20 mm cellulose acetate flavor.

EXAMPLE XIX Flavor Utility of Isobutyric Acid Ester of C₁₁ UnsaturatedAlcohol

The following raisin-rum flavor formulation is prepared:

    ______________________________________                                        Ingredients          Parts by Weight                                          ______________________________________                                        Natural rum essence  48                                                       Citral               2.8                                                      Carvone              2.4                                                      Alpha-terpinene      2.4                                                      Alpha-fenchyl alcohol                                                                              3.8                                                      Geranyl acetone      2.4                                                      Nootkatone           5.4                                                      Neryl acetate        3.6                                                      Natural lemon oil, terpineless                                                                     12.3                                                     Mixture prepared according to                                                                      24.0                                                     Example IV containing the mixture                                             defined according to the generic                                              structure:                                                                     ##STR112##                                                                   wherein in said mixture, one of                                               the dashed lines represents a                                                 carbon-carbon double bond and                                                 each of the other of the dashed                                               lines represent carbon-carbon                                                 single bonds.                                                                 Beta-hydroxy butyric acid                                                                          4.2                                                      Natural grape essence                                                                              2.0                                                      ______________________________________                                    

The flavor formulation is compared to the same flavor formulationwithout the mixture of compounds defined according to the structure:##STR113## wherein the dashed lines are defined as above. Each of theformulations is compared at the rate of 50 parts per million in astandard vanilla ice cream. Each of the formulations is also comparedseparately in water at the rate of 5 parts per million. Side by side,the formulations with and without the compound defined according to thestructure: ##STR114## give rise to the conclusion that the flavorformulation containing the mixture of compounds defined according to thestructure: ##STR115## is greatly improved over the formulation withoutthat mixture. The formulation containing the mixture defined accordingto the structure: ##STR116## has a definite, more natural, more intense(five fold) rum-raisin nuance than the formulation without said mixturewhich is bland and relatively "synthetic tasting". In general, a benchpanel of 5 members unanimously prefers the formulation containing themixture of compounds defined according to the structure: ##STR117##

When the mixture of compounds defined according to the structure:##STR118## is replaced by the pure compound having the structure:##STR119## prepared by high pressure liquid chromatography separation ofthe foregoing mixture, the same result ensues.

EXAMPLE XX

A. Powder Flavor Formulation

20 grams of the flavor composition of Example XIX is emulsified in asolution containing 300 grams of gum acacia and 70 grams water. Theemulsion is spray-dried with a Bowen Lab Model Drier utilizing 260c.f.m. of air with an inlet temperature of 500° F., an outlettemperature of 200° F. and a wheel speed of 50,000 rpm.

B. Sustained Release Flavor

    ______________________________________                                                            Parts by Weight                                           ______________________________________                                        Ingredients                                                                   Liquid lemon flavor of                                                                             20                                                       Example XIX                                                                   Propylene glycol     9                                                        Cab-O-Sil ® M-5  5.00                                                     (Brand of Silica produced by                                                  the Cabot Corporation of                                                      125 High Street, Boston,                                                      Mass. 02110                                                                   Physical properties:                                                          Surface area: 200 m.sup.2 /gm                                                 Nominal particle size 0.012 microns                                           Density: 2.3 lbs/cu. ft.)                                                     ______________________________________                                    

The Cab-O-Sil® is dispersed in the liquid rum-raisin flavor compositionof Example XIX with vigorous stirring, thereby resulting in a viscousliquid. 71 parts by weight of the powder flavor composition of Part A,supra, is then blended into the said viscous liquid, with stirring, at25° C., for a period of 30 minutes resulting in a dry, free-flowingsustained release flavor powder.

EXAMPLE XXI

10 parts by weight of 50 Bloom pigskin gelatin is added to 90 parts byweight of water at a temperature of 150° F. The mixture is agitateduntil the gelatin is completely dissolved and the solution is cooled to120° F. 20 parts by weight of the liquid flavor composition of ExampleXIX is added to the solution which is then homogenized to form anemulsion having particle size typically in the range of 2-5 microns.This material is kept at 120° F. under which conditions the gelatin willnot jell.

Coacervation is induced by adding, slowly and uniformly 40 parts byweight of a 20% aqueous solution of sodium sulfate. During coacervation,the gelatin molecules are deposited uniformly about each oil droplet asa nucleus.

Gelation is effected by pouring the heated coacervate mixture into 1,000parts by weight of 7% aqueous solution of sodium sulfate at 65° F. Theresulting jelled coacervate may be filtered and washed with water attemperatures below the melting point of gelatin, to remove the salt.

Hardening of the filtered cake, in this example, is effected by washingwith 200 parts by weight of 37% solution of formaldehyde in water. Thecake is then washed to remove residual formaldehyde.

EXAMPLE XXII Chewing Gum

100 Parts by weight of chicle are mixed with 4 parts by weight of theflavor prepared in accordance with Example XX. 300 Parts of sucrose and100 parts of corn syrup are added. Mixing is effected in a ribbonblender with jacketed side walls of the type manufactured by the BakerPerkins Co.

The resultant chewing gum blend is then manufactured into strips 1 inchin width and 0.1 inches in thickness. The strips are cut into lengths of3 inches each. On chewing, the chewing gum has a pleasant, long lasting"rum-raisin" flavor.

EXAMPLE XXIII Chewing Gum

100 Parts by weight of chicle are mixed with 18 parts by weight of theflavor prepared in accordance with Example XX. 300 Parts of sucrose and100 parts of corn syrup are then added. Mixing is effected in a ribbonblender with jacketed side walls of the type manufactured by the BakerPerkins Co.

The resultant chewing gum blend is then manufactured into strips 1 inchin width and 0.1 inches in thickness. The strips are cut into lengths of3 inches each. On chewing, the chewing gum has a pleasant, long lastingrum-raisin flavor.

EXAMPLE XXIV Toothpaste Formulation

The following separate groups of ingredients are prepared:

    ______________________________________                                        Parts by Weight                                                                              Ingredient                                                     ______________________________________                                        Group "A"                                                                     30.200         Glycerine                                                      15.325         Distilled Water                                                 .100          Sodium Benzoate                                                 .125          Saccharin Sodium                                                .400          Stannous Fluoride                                              Group "B"                                                                     12.500         Calcium Carbonate                                              37.200         Dicalcium Phosphate                                                           (Dihydrate)                                                    Group "C"                                                                     2.000          Sodium N--Luaroyl Sarcosinate                                                 (foaming agent)                                                Group "D"                                                                     1.200          Flavor Material of Example                                                    XX                                                             100.00 (Total)                                                                ______________________________________                                    

PROCEDURE:

1. The ingredients in Group "A" are stirred and heated in a steamjacketed kettle to 160° F.

2. Stirring is continued for an additional three to five minutes to forma homogeneous gel

3. The powders of Group "B" are added to the gel, while mixing, until ahomogeneous paste is formed.

4. With stirring, the flavor of "D" is added and lastly the sodiumn-lauroyl sarcosinate

5. The resultant slurry is then blended for one hour. The completedpaste is then transferred to a three roller mill and then homogenized,and finally tubed.

The resulting toothpaste when used in a normal toothbrushing procedureyields a pleasant rum-raisin flavor of constant strong intensitythroughout said procedure (1-1.5 minutes).

EXAMPLE XXV Chewable Vitamin Tablets

The flavor material produced according to the process of Example XX isadded to a Chewable Vitamin Tablet Formulation at a rate of 10 gm/Kgwhich chewable vitamin tablet formulation is prepared as follows:

In a Hobart Mixer, the following materials are blended to homogeneity:

    ______________________________________                                                           Gms/1000 Tablets                                           ______________________________________                                        Vitamin C (ascorbic acid) as                                                                       70.00                                                    ascorbic acid-sodium mixture 1:1                                              Vitamin B (thiamine mononitrate)                                                                   4.0                                                      as Rocoat ® thiamine mononitrate                                          331/3% (Hoffman La Roche)                                                     Vitamin B.sub.2 (riboflavin) as Rocoat ®                                                       5.0                                                      riboflavin 331/3%                                                             Vitamin B.sub.6 (pyridoxine Hydrochloride                                                          4.0                                                      as Rocoat ® pyridoxine hydrochloride                                      331/3%                                                                        Niacinamide as Rocoat ® niacinamide                                                            33.0                                                     331/3%                                                                        Calcium pantothenate 11.5                                                     Vitamin B.sub.12 (cyanocobalamin) as                                                               3.5                                                      Merck 0.1% in gelatin                                                         Vitamin E (dl-alpha tocopheryl acetate)                                                            6.6                                                      as dry Vitamin E acetate 331/3% Roche                                         d-Biotin             0.044                                                    Flavor of Example XX (as indicated above)                                     Certified lake color 5.0                                                      Sweetener - sodium saccharin                                                                       1.0                                                      Magnesium stearate lubricant                                                                       10.0                                                     Mannitol q.s. to make                                                                              500.0                                                    ______________________________________                                    

Preliminary tablets are prepared by slugging with flat-faced punches andgrinding the slugs to 14 mesh. 13.5 G dry Vitamin A acetate and 0.6 gVitamin D are then added as beadlets. The entire blend is thencompressed using concave punches at 0.5 g each.

Chewing of the resultant tablets yields a pleasant, long-lasting,consistently strong rum-raisin flavor with a tropical fruit-likebackground for a period of 12 minutes.

What is claimed is:
 1. A mixture of pyrones defined according to thegeneric structure: ##STR120## wherein in the mixture in each of themolecules one of the dashed lines represents a carbon-carbon double bondand each of the other of the dashed lines represents a carbon-carbonsingle bond, produced according to the process comprising the step ofintimately admixing one or a mixture of diisoamylene derivatives definedaccording to the genus: ##STR121## wherein one of the dashed linesrepresents a carbon-carbon double bond and each of the other of thedashed lines represents a carbon-carbon single bond or a compound havinga structure selected from the group consisting of ##STR122## withformaldehyde or a formaldehyde precursor selected from the groupconsisting of trioxane, paraformaldehyde and formalin, the reactionbeing carried out in the presence of a protonic acid catalyst selectedfrom the group consisting of sulfuric acid, phosphoric acid, partoluenesulphonic acid and methane sulphone acid, the reaction being carried outusing a mole ratio of effective formaldehyde:diisoamylene derivative offrom 2:1 up to 1:2, the concentration of protonic acid in the reactionmass varying from about 0.01 moles per liter up to about 1 mole perliter; the reaction being carried out in the presence of an acylanhydride having the structure: ##STR123## wherein R₁ and R₂ are thesame or different and each represents C₁ -C₃ alkyl; the mole ratio ofacyl anhydride:diisoamylene derivative varying from about 1:4 up toabout 1:1; the reaction temperature varying from about 50° C. up toabout 120° C.; and then recovering by means of fractional distillation,the said mixture of pyrones defined according to the generic structure:##STR124##